Luminescent diazabenzimidazole carbene metal complexes

ABSTRACT

The present invention relates to metal-carbene complexes of the general formula 
     
       
         
         
             
             
         
       
     
     to organic electronic devices, especially OLEDs (Organic Light-Emitting Diodes) which comprise such complexes, to an apparatus selected from the group consisting of illuminating elements, stationary visual display units and mobile visual display units comprising such an OLED, to the use of such a metal-carbene complex in OLEDs, for example as emitter, matrix material, charge transport material and/or charge or exciton blocker

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a divisional application of, and claimspriority to, U.S. patent application Ser. No. 14/908,606, filed Jan. 29,2016, now U.S. Pat. No. 9,673,408, which is a 35 U.S.C. §371 nationalphase application from, and claiming priority to, InternationalApplication PCT/EP2014/066272, filed Jul. 29, 2014, which claimspriority under 35 U.S.C. §119(a)-(d) to European Application Nos.13178675.8, filed Jul. 31, 2013, and 14175848.2, filed Jul. 4, 2014, allof which applications are incorporated herein by reference in theirentireties.

DESCRIPTION

The present invention relates to metal-carbene complexes of the generalformula (I), to organic electronic devices, especially OLEDs (OrganicLight-Emitting Diodes) which comprise such complexes, to an apparatusselected from the group consisting of illuminating elements, stationaryvisual display units and mobile visual display units comprising such anOLED, to the use of such a metal-carbene complex in OLEDs, for exampleas emitter, matrix material, charge transport material and/or charge orexciton blocker.

Organic light-emitting diodes (OLEDs) exploit the propensity ofmaterials to emit light when they are excited by electrical current.OLEDs are of particular interest as an alternative to cathode ray tubesand liquid-crystal displays for production of flat visual display units.

Owing to the very compact design and the intrinsically low powerconsumption, devices comprising OLEDs are suitable especially for mobileapplications, for example for applications in cellphones, smartphones,digital cameras, mp3 players, laptops, etc. In addition, white OLEDsgive great advantages over the illumination technologies known to date,especially a particularly high efficiency.

The prior art proposes numerous materials which emit light on excitationby electrical current.

EP1956008 relates to organic compounds represented by formula

and charge-transporting materials composed of the compounds.

WO2005/019373 discloses transition metal complexes with carbene ligandsas emitters for organic light emitting diodes (OLEDs). The ligands ofthese transition metal complexes are preferably attached via ametal-carbene bond and via a bond between the metal atom and an aromaticradical. Numerous heterocycles attached to the metal atom via a carbenebond are disclosed, but no complexes which havediazabenzimidazolocarbene ligands are disclosed.

WO2006/056418A2 discloses the use of transition metal-carbene complexesin organic light-emitting diodes. In the corresponding transition metalcomplexes, a metal atom is bonded to the ligands via at least onemetal-carbene bond and via a bond between the metal atom and an aromaticradical. The metal-carbene bond is preferably bonded via an imidazolering, to which, according to the document cited, aromatic cycles mayalso be fused. However, no complexes which havediazabenzimidazolocarbene ligands are disclosed.

WO2007/088093A1 and WO2007/185981A1 disclose transition metalcomplexescomprising ligands attached via metal-carbene bonds. Preferred carbeneligands mentioned are imidazole ligands. These may also have fusedaromatic six-membered rings, where 1 to 4 of the carbon atoms present inthe aromatic six-membered ring may be replaced by nitrogen. Thedocuments cited do not disclose the positions of the nitrogens in thearomatic six-membered ring.

WO2007/1115970A1 likewise discloses transition metal-carbene complexes,preference being given to imidazole units as the carbene ligand. Anaromatic six-membered ring may likewise be fused to this imidazole unit,wherein 1 to 4 carbon atoms may be replaced by nitrogen atoms. Thisdocument does not comprise any disclosure as to the position of thenitrogen atoms.

KR2012/0135837, KR2013/0043342, WO2012/170463 and WO12/172482 relate tometal-carbene complexes comprising a central atom selected from iridiumand platinum, and specific azabenzimidazolocarbene ligands and to OLEDs,which comprise such complexes. US2012/0305894, WO2012/170461,WO2012/121936 and US2013/032766 (WO2011/073149) relate to metal-carbenecomplexes comprising a central atom selected from iridium and platinum,and diazabenzimidazolocarbene ligands, to organic light diodes whichcomprise such complexes and to light-emitting layers comprising at leastone such metal-carbene complex. However, no complexes which havediazabenzimidazolocarbene ligands, wherein the phenyl group bonded tothe Ir atom is substituted by a dialkylphenyl group, are disclosed bysaid documents.

It is an object of the present invention to provide organic electronicdevices, preferably OLEDs, having—compared with the organic electronicdevices known in the art—a high color purity in the blue region of thevisible electromagnetic spectrum, a high efficiency, low voltage and/orimproved lifetime/stability.

Surprisingly, it was found that substitution of the cyclometallatingN-aryl group of the diazabenzimidazole carbene ligand by an optionallysubstituted aryl group R can result in a decrease of the lifetime of theluminescence (τ_(v)) and increase of the radiative rate k_(rad) of therespective Pt, or Ir carbene complexes, comprising at least one ligandof formula

These metal-carbene complexes may spend less time in the excited state,thereby decreasing the possibility for photochemical reactions, orquenching to occur. Therefore, these compounds may provide devices withimproved stability and/or also improved device efficiency. In addition,the inventive metal-carbene complexes may provide reduced color-shift ofthe emission with increasing doping concentration of the compounds in ahost material.

The ligands of formula

can be used for the production of metal carbene-complexes, especially Ptand Ir carbene complexes. The metal carbene-complexes may have reducedlifetime of luminescence.

It has been further found by the inventors of the present invention thatOLEDs comprising the metal-carbene complexes of formula (I) according tothe present invention in an organic electronic device, preferably in anOLED, especially as an emitter material in an OLED, show improved deviceperformance such as high quantum efficiency, high luminous efficacy, lowvoltage, good stabilities and/or long lifetimes. The metal-carbenecomplexes of formula (I) are particularly suitable as emitter materialswith an emission in the blue region with a CIE-y color coordinate below0.42, especially below 0.38, which enables for example the production ofwhite OLEDs, or full-color displays.

The objects of the present invention are achieved by metal-carbenecomplexes of the general formula

M is Pt, or Ir;

if M is Ir, m is 1, 2, or 3; o is 0, 1, or 2; and the sum of m+o is 3;with the proviso that, if o=2, the ligands L may be the same ordifferent;if M is Pt, m is 1, or 2; o is 0, or 1; and the sum of m+o is 2;L is a monoanionic bidentate ligand,R is a group of formula R

R′ is H, C₁-C₅alkyl group, or a fluoroC₁-C₄alkyl group;R¹ is H, a C₁-C₅alkyl group, a fluoroC₁-C₄alkyl group, or aC₃-C₆cycloalkyl group,R² is H, a C₁-C₅alkyl group, a fluoroC₁-C₄alkyl group, or aC₃-C₆cycloalkyl group,R³, R^(3′) and R^(3″) are independently of each other hydrogen; aC₁-C₁₈alkyl group, which can optionally be substituted by E and/orinterrupted by D; a C₃-C₁₂cycloalkyl group, which can optionally besubstituted by G; a C₃-C₁₀heterocycloalkyl radical which is interruptedby at least one of O, S and NR⁶⁵ and/or substituted by E; a C₆-C₂₄arylgroup, which can optionally be substituted by G; or a C₂-C₃₀heteroarylgroup, which can optionally be substituted by G; a halogen atom,especially F or Cl; CF₃, CN, or SiR⁸⁰R⁸¹R⁸²;R³ and R^(3′), or R¹ and R^(3′) together form a group of formula

wherein X is O, S, NR⁷⁵ or CR⁷³R⁷⁴;R⁴, R^(4′) and R⁵ are independently of each other hydrogen; aC₁-C₁₈alkyl group, which can optionally be substituted by E and/orinterrupted by D; a C₃-C₁₂cycloalkyl group, which can optionally besubstituted by E; a C₃-C₁₀heterocycloalkyl radical which is interruptedby at least one of O, S and NR⁶⁵ and/or substituted by E; a C₆-C₁₄arylgroup, which can optionally be substituted by G; or a C₂-C₁₀heteroarylgroup, which can optionally be substituted by G; a halogen atom,especially F or Cl; CF₃, CN, or SiR⁸⁰R⁸¹R⁸²; orR⁴ and R^(4′) together form a group of formula

R⁶ and R⁷ are independently of each other hydrogen, a C₁-C₈alkyl group,optionally interrupted by at least one heteroatom selected from —O—, —S—and —NR⁶⁵—, optionally bearing at least one substituent, which isselected from the group consisting of C₁-C₈alkyl, C₁-C₈alkoxy, halogen,preferably F, and C₁-C₈haloalkyl, such as CF₃; a C₃-C₆cycloalkyl group,optionally bearing at least one substituent, which is selected from thegroup consisting of C₁-C₈alkyl, C₁-C₈alkoxy, halogen, preferably F,C₁-C₈haloalkyl, such as CF₃; a heteroC₃-C₆cyclo alkyl group, interruptedby at least one heteroatom selected from —O—, —S— and —NR⁶⁵—, optionallybearing at least one substituent, which is selected from C₁-C₈alkyl,C₁-C₈alkoxy, halogen, preferably F, C₁-C₈haloalkyl, such as CF₃; or aC₆-C₁₄arylgroup, which can optionally be substituted by one, or twoC₁-C₈alkyl groups; orR⁶ and R⁷ form together a ring

wherein A21, A21′, A22, A22′, A23, A23′, A24′ and A24 are independentlyof each other H, a C₁-C₄alkyl group, a C₃-C₆cycloalkyl group, afluoroC₁-C₄alkyl group;D is —CO—, —COO—, —S—, —SO—, —SO₂—, —O—, —NR⁶⁵—, —SiR⁷⁰R⁷¹—, —POR⁷²—,—CR⁶³═CR⁶⁴—, or —C≡C—, E is —OR⁶⁹, —SR⁶⁹, —NR⁶⁵R⁶⁶, —COR⁶⁸, —COOR⁶⁷,—CONR⁶⁵R⁶⁶, —CN, or F;G is E, or a C₁-C₁₈alkyl group, a C₆-C₁₄aryl group, a C₆-C₁₄aryl group,which is substituted by F, C₁-C₁₈alkyl, or C₁-C₁₈alkyl, which issubstituted by F and/or interrupted by O; a C₂-C₁₀heteroaryl group, or aC₂-C₁₀heteroaryl group, which is substituted by F, C₁-C₁₈alkyl,SiR⁸⁰R⁸¹R⁸², or C₁-C₁₈alkyl which is substituted by F and/or interruptedby O;R⁶³ and R⁶⁴ are independently of each other H, C₆-C₁₈aryl; C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; orC₁-C₁₈alkyl which is interrupted by —O—;R⁶⁵ and R⁶⁶ are independently of each other a C₆-C₁₈aryl group; aC₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; aC₁-C₁₈alkyl group; or a C₁-C₁₈alkyl group, which is interrupted by —O—;or R⁶⁵ and R⁶⁶ together form a five or six membered ring, R⁶⁷ is aC₆-C₁₈aryl group; a C₆-C₁₈aryl group, which is substituted byC₁-C₁₈alkyl, or C₁-C₁₈alkoxy; a C₁-C₁₈alkyl group; or a C₁-C₁₈alkylgroup, which is interrupted by —O—, R⁶⁸ is H; a C₆-C₁₈aryl group; aC₆-C₁₈aryl group, which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy;a C₁-C₁₈alkyl group; or a C₁-C₁₈alkyl group, which is interrupted by—O—,R⁶⁹ is a C₆-C₁₈aryl; a C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl,or C₁-C₁₈alkoxy; a C₁-C₁₈alkyl group; or a C₁-C₁₈alkyl group, which isinterrupted by —O—,R⁷⁰ and R⁷¹ are independently of each other a C₁-C₁₈alkyl group, aC₆-C₁₈aryl group, or a C₆-C₁₈aryl group, which is substituted byC₁-C₁₈alkyl, andR⁷² is a C₁-C₁₈alkyl group, a C₆-C₁₈aryl group, or a C₆-C₁₈aryl group,which is substituted by C₁-C₁₈alkyl,R⁷³ and R⁷⁴ are independently of each other H, C₁-C₂₅alkyl, C₁-C₂₅alkylwhich is interrupted by O, C₇-C₂₅arylalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl whichis substituted by C₁-C₁₈alkyl, C₂-C₂₀heteroaryl, or C₂-C₂₀heteroarylwhich is substituted by C₁-C₁₈alkyl;R⁷³ and R⁷⁴ together form a group of formula ═CR⁷⁶R⁷⁷, whereinR⁷⁶ and R⁷⁷ are independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkylwhich is interrupted by O, C₆-C₂₄aryl, C₆-C₂₄aryl which is substitutedby C₁-C₁₈alkyl, or C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl which issubstituted by C₁-C₁₈alkyl, orR⁷³ and R⁷⁴ together form a five or six membered ring, which optionallycan be substituted by C₁-C₁₈alkyl, C₁-C₁₈alkyl which is interrupted byO, andR⁷⁵ is a C₆-C₁₈aryl group; a C₆-C₁₈aryl which is substituted byC₁-C₁₈alkyl, or C₁-C₁₈alkoxy;a C₁-C₁₈alkyl group; or a C₁-C₁₈alkyl group, which is interrupted by—O—, andR⁸⁰, R⁸¹ and R⁸² are independently of each other a C₁-C₂₅alkyl group,which can optionally be interrupted by O; a C₆-C₁₄arylgroup, which canoptionally be substituted by C₁-C₁₈alkyl;or a C₂-C₁₀heteroaryl group, which can optionally be substituted byC₁-C₁₈alkyl.

FIG. 1 provides a plot of the EL intensity of compounds CC-1 and C-127as a function of wavelength.

R′ is H, a C₁-C₅alkyl group, or a fluoroC₁-C₄alkyl group; preferably H,or a C₁-C₅alkyl group, more preferably H.

If R′ is a C₁-C₅alkyl group, or a fluoroC₁-C₄alkyl group the followingpreferences apply:

R¹ and R^(4′) are the same.

R⁴ and R⁵ are H.

R¹ and R² are H, or—which case is more preferred—one of R¹ and R² is Hand the other is different from H and is preferably a C₁-C₅alkyl group.

Examples of metal-carbene complexes of the general formula (I), whereinR′ is a C₁-C₅alkyl group are shown below:

R is a group of formula

R¹ is H, a C₁-C₅alkyl group, a fluoroC₁-C₄alkyl group, or aC₃-C₆cycloalkyl group, especially H, a C₁-C₅alkyl group, a cyclopentyl,or cyclohexyl group; very especially a C₁-C₅alkyl group, a cyclopentylor cyclohexyl group.

R² is H, a C₁-C₅alkyl group, a fluoroC₁-C₄alkyl group, or aC₃-C₆cycloalkyl group, especially H, a C₁-C₅alkyl group, a cyclopentyl,or cyclohexyl group; very especially a C₁-C₅alkyl group, a cyclopentylor cyclohexyl group.

If R³ and R^(3′) represent a halogen atom, they are preferably F or Cl,more preferably F.

If R³ and R^(3′) represent a group of formula SiR⁷⁰R⁷¹R⁷² they arepreferably Si(CH₃)₃, Si(Ph)₃, or SiPh₂tBu; with the proviso that onlyone of R³ and R^(3′) is SiR⁷⁰R⁷¹R⁷², and the other is H.

The heteroaryl radical R³, R^(3′) and R^(3″) is, for example, selectedfrom the group consisting of pyridyl, methylpyridyl, pyrimidyl,pyrazinyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, indolyl,methylindolyl, benzofuranyl and benzothiophenyl, which can optionally besubstituted by one, or more groups selected from a C₁-C₄alkyl group, aC₃-C₆cycloalkyl group and a C₁-C₄fluoroalkyl group; especiallycarbazolyl, dibenzofuranyl, dibenzothiophenyl, which can optionally besubstituted by one, or more groups selected from a C₁-C₄alkyl group, aC₃-C₆cycloalkyl group and a C₁-C₄fluoroalkyl group; more especiallydibenzofuranyl, dibenzothiophenyl, which can optionally be substitutedby one, or more groups selected from a C₁-C₄alkyl group, and aC₃-C₆cycloalkyl group.

If R³, R^(3′) and R^(3″) represent a C₆-C₁₄aryl group, they are, forexample, a phenyl group, which can optionally be substituted by one, ormore groups selected from a C₁-C₄alkyl group, a C₃-C₆cycloalkyl groupand a fluoroC₁-C₄alkyl group.

R³ is preferably H, a C₁-C₅alkyl group, a cyclopentyl or cyclohexylgroup, a group of formula

wherein R¹⁰ is H, or a C₁-C₅alkyl group, R¹¹ is H, or a C₁-C₅alkylgroup, R¹² is a C₁-C₅alkyl group, and R^(12′) is a C₁-C₅alkyl group.

R^(3′) is preferably H, a C₁-C₅alkyl group, a cyclopentyl or cyclohexylgroup.

R^(3″) is preferably H, a C₁-C₅alkyl group, a cyclopentyl or cyclohexylgroup.

R⁴, R^(4′) and R⁵ are preferably independently of each other hydrogen, aC₁-C₅alkyl group, a C₆-C₁₄aryl group, which can optionally besubstituted by one, or more groups selected from a C₁-C₄alkyl group anda fluoroC₁-C₄alkyl group; or a heteroaryl radical selected from thegroup consisting of pyridyl, methylpyridyl, pyrimidyl, pyrazinyl,carbazolyl, dibenzofuranyl, dibenzothiophenyl, indolyl, methylindolyl,benzofuranyl and benzothiophenyl, which can optionally be substituted byone, or more groups selected from a C₁-C₄alkyl group, a C₃-C₆cycloalkylgroup and a C₁-C₄fluoroalkyl group; more preferably independently ofeach other hydrogen, a C₁-C₅alkyl group, a C₆-C₁₄aryl group, which canoptionally be substituted by one, or more groups selected from aC₁-C₄alkyl group and a fluoroC₁-C₄alkyl group.

Preferably, R⁶ and R⁷ are independently of each other H, a C₁-C₈alkylgroup, or a C₃-C₆cycloalkyl group, or a C₆-C₁₄arylgroup, which canoptionally be substituted by one, or two C₁-C₈alkyl groups, or R⁶ and R⁷form together a ring

Examples of a C₆-C₁₄arylgroup are a group of formula

whereinR²² and R²³ are independently of each other H, especially a C₁-C₅alkylgroup, a cyclopentyl or cyclohexyl group;R²⁴ is H, or a C₁-C₅alkyl group;R²⁵ is H, especially a C₁-C₅alkyl group, a cyclopentyl or cyclohexylgroup;R²⁶ is H, a C₁-C₅alkyl group, a cyclopentyl or cyclohexyl group; andR²⁷ is H, a C₁-C₅alkyl group, a cyclopentyl or cyclohexyl group; withthe proviso that in case one of R²⁶ and R²⁷ is a cyclopentyl orcyclohexyl group, the other is H. More preferably, R⁶ is H, a C₁-C₄alkylgroup, or a C₃-C₆cycloalkyl group and R⁷ is H; or R⁶ is H, and R⁷ is aC₁-C₄alkyl group, or a C₃-C₆cycloalkyl group.

If two monoanionic bidentate ligands L are present, they can bedifferent, but are preferably the same. The monoanionic bidentate ligandL in the metal-carbene complex has the following meaning:

a ligand of formula (A)

in whichR⁵¹ is in each case independently a linear or branched C₁-C₆alkyl group,preferably methyl, ethyl, isopropyl or tert-butyl; a substituted orunsubstituted C₆-C₁₈aryl radical, preferably an unsubstituted phenyl or2,6-diC₁-C₈alkylphenyl; a substituted or unsubstituted C₆-C₁₂heteroaryl,R⁵² is hydrogen; a linear or branched C₁-C₆alkyl group; a substituted orunsubstituted C₆-C₁₈aryl radical; preferably hydrogen or2,6-dimethylphenyl; where the ligand of the formula (A) is preferablyacetylacetonato (in case of ligand A, o is 1); orL is a carbene ligand of the general formula (B)

whereA^(9′) is CR^(12′) or N;A^(10′) is CR^(13′) or N;R^(11′) is a linear or branched, substituted or unsubstituted alkylradical having 1 to 20 carbon atoms, optionally interrupted by at leastone heteroatom, selected from O, S and N; a substituted or unsubstitutedcycloalkyl radical having 3 to 18 carbon atoms; a substituted orunsubstituted heterocycloalkyl radical interrupted by at least oneheteroatom, selected from O, S and N, and having 3 to 18 carbon atomsand/or heteroatoms; a substituted or unsubstituted aryl radical having 6to 30 carbon atoms, a substituted or unsubstituted heteroaryl radicalinterrupted by at least one heteroatom, selected from O, S and N andhaving a total of 5 to 30 carbon atoms and/or heteroatoms;R^(12′) and R^(13′) are each independently hydrogen; deuterium; a linearor branched, substituted or unsubstituted alkyl radical having 1 to 20carbon atoms, optionally interrupted by at least one heteroatom,selected from O, S and N; a substituted or unsubstituted cycloalkylradical having 3 to 18 carbon atoms; a substituted or unsubstitutedheterocycloalkyl radical interrupted by at least one heteroatom,selected from O, S and N, and having 3 to 18 carbon atoms and/orheteroatoms; a substituted or unsubstituted aryl radical having 6 to 30carbon atoms; a substituted or unsubstituted heteroaryl radicalinterrupted by at least one heteroatom, selected from O, S and N andhaving a total of 5 to 30 carbon atoms and/or heteroatoms; or a groupwith donor or acceptor action;if A^(9′) is CR^(12′) and A^(10′) is CR^(13′), CR^(12′) and CR^(13′)together may form, a saturated or unsaturated or aromatic, optionallysubstituted ring, which is optionally interrupted by at least oneheteroatom, selected from O, S and N, has a total of from 5 to 18 carbonatoms and/or heteroatoms, and may optionally be fused to at least onefurther optionally substituted saturated or unsaturated or aromaticring, optionally interrupted by at least one heteroatom, selected fromO, S and N, and having a total of from 5 to 18 carbon atoms and/orheteroatoms;A^(5′) is CR^(14′) or N;A^(6′) is CR^(15′) or N;A^(7′) is CR^(16′) or N;A^(8′) is CR^(17′) or N;R^(14′), R^(15′), R^(16′) and R^(17′) are each independently hydrogen;deuterium; a linear or branched, substituted or unsubstituted alkylradical having 1 to 20 carbon atoms, optionally interrupted by at leastone heteroatom, selected from O, S and N; a substituted or unsubstitutedcycloalkyl radical having 3 to 18 carbon atoms; a substituted orunsubstituted heterocycloalkyl radical interrupted by at least oneheteroatom, selected from O, S and N, and having 3 to 18 carbon atomsand/or heteroatoms; a substituted or unsubstituted aryl radical having 6to 30 carbon atoms; a substituted or unsubstituted heteroaryl radicalinterrupted by at least one heteroatom, selected from O, S and N andhaving a total of 5 to 30 carbon atoms and/or heteroatoms; or a groupwith donor or acceptor action; orR^(14′) and R^(15′), R^(15′) and R^(16′) or R^(16′) and R^(17′) mayform, together with the carbon atoms to which they are bonded, asaturated or unsaturated or aromatic, optionally substituted ring, whichis optionally interrupted by at least one heteroatom, selected from O, Sand N, has a total of from 5 to 18 carbon atoms and/or heteroatoms, andmay optionally be fused to at least one further optionally substitutedsaturated or unsaturated or aromatic ring, optionally interrupted by atleast one heteroatom, selected from O, S and N, and having a total offrom 5 to 18 carbon atoms and/or heteroatoms; or if A^(9′) is CR^(12′),R^(12′) and R^(17′) together may form a saturated or unsaturated, linearor branched bridge optionally comprising heteroatoms, selected from O, Sand N, to which is optionally fused a substituted or unsubstituted,five- to eight-membered ring comprising carbon atoms and/or heteroatoms,and which are optionally substituted with aromatic units, heteroaromaticunits or groups with donor or acceptor action (in case of ligand B, o is2);q′ is 0 or 1; orL is a ligand of the general formula (C)

in which the symbols are each defined as follows:D¹ are each independently CR^(34″′) or N;

W is C or N;

E¹ are each independently CR^(35″′), N, NR^(36″′) or O;

I is 1 or 2;

R^(34″′), R^(35″′), R^(36′″) are each independently hydrogen;substituted or unsubstituted or branched alkyl; substituted orunsubstituted aryl or substituted or unsubstituted heteroaryl; or ineach case two R^(34″′), R^(35″′) or R^(36″′) radicals together form afused ring which may optionally comprise at least one heteroatom; orR^(34″′), R^(35″′), R^(36″′) or R^(37″′) is a radical having donor oracceptor action;where the dotted line means an optional bridge between one of the Dgroups and one of the E groups; where the bridge may be defined asfollows:alkylene, arylene, heteroarylene, alkynylene, alkenylene, NR^(38″′), O,S, SiR^(41′″)R^(42″′), and (CR^(43′″)R^(44″′))_(v), where one or morenonadjacent (CR^(43′″)R^(44″′)) groups may be replaced by NR^(38″′), O,S, SiR^(41′″)R^(42″′), where v is from 2 to 10; andR^(38′″), R^(41′″), R^(42″′), R^(43′″), R^(44′″) are each H, alkyl, arylor heteroaryl.

L is preferably a ligand of formula (B), or (C), more preferably aligand of formula (B), if M is Ir.

L is preferably a group (X-1), (X-2), (X-3), (X-4), (X-5), (X-6), (X-7),(X-8), (X-9), (X-10), (X-11), (X-12), (X-13), (X-14), (X-15), (X-16),(X-17), (X-18), (X-19), (X-20), (X-21), (X-22), (X-23), (X-24), (X-25),(X-26), or (X-27) as defined in claim 10; more preferably a group (X-1),(X-2), (X-3), or (X-4). The synthesis and use of the ligands (X-1) to(X-27) for the preparation of metal complexes is, for example, describedin WO2006121811, US20110057559, WO2011106344, WO2012048266,WO2007095118, WO2008156879, WO2010068876, WO2011157339, andWO2010086089.

In addition, In principal, the ligand L can also be a ligand R (D′)

which is different from the ligand

wherein Z¹ and Z² are N, or Z¹ and Z² are CH; R* has the meaning of R′,R⁵⁴ has the meaning of R⁴, R^(54′) has the meaning of R^(4′), R⁵⁵ hasthe meaning of R⁵, R⁵⁶ has the meaning of R⁶ and R⁵⁷ has the meaning ofR⁷ and each group R is the same within one metal-carbene complex. Insaid embodiment the present invention is directed to complexes offormula D₂MD′ (Va), or D₂MD′ (Vb). Complexes of formula D₂MD′ (Va) arepreferred.

-   For R*, R⁵⁴, R^(54′), R⁵⁵, R⁵⁶ and R⁵⁷ the same preferences apply as    for R¹, R⁴, R^(4′), R⁵, R⁶ and R⁷, respectively.

The metal-carbene complex is preferably a metal-carbene complex offormula

whereinR is a group of formula

R′ is H, or a C₁-C₅alkyl group, especially ethyl, isopropyl, orisobutyl; very especially H; and M, m, o, L, R¹, R², R³, R^(3′), R^(3″),R⁴, R^(4′), R⁵, R⁶ and R⁷ are as defined above.

Metal complexes of formula D₂ML and D₃M are more preferred than metalcomplexes of formula DML₂, such as, for example,

and

because, in general, the decrease of lifetime of luminescence in case ofmetal complexes of formula D₂ML and D₃M is more pronounced.

The metal-carbene complex is more preferably a metal-carbene complex offormula

whereinR is a group of formula

andR⁶ in formula (IIa) is a C₁-C₈alkyl group, optionally interrupted by atleast one heteroatom selected from —O—, —S— and —NR⁶⁵—, optionallybearing at least one substituent, which is selected from the groupconsisting of C₁-C₈alkyl, C₁-C₈alkoxy, halogen, preferably F, andC₁-C₈haloalkyl, such as CF₃; a C₃-C₆cycloalkyl group, optionally bearingat least one substituent, which is selected from the group consisting ofC₁-C₈alkyl, C₁-C₈alkoxy, halogen, preferably F, C₁-C₈haloalkyl, such asCF₃; a heteroC₃-C₆cyclo alkyl group, interrupted by at least oneheteroatom selected from —O—, —S— and —NR⁶⁵—, optionally bearing atleast one substituent, which is selected from C₁-C₈alkyl, C₁-C₈alkoxy,halogen, preferably F, C₁-C₈haloalkyl, such as CF₃; or a group offormula

R²² and R²³ are independently of each other H, especially a C₁-C₅alkylgroup, a cyclopentyl or cyclohexyl group;R²⁴ is H, or a C₁-C₅alkyl group;R²⁵ is H, especially a C₁-C₅alkyl group, a cyclopentyl or cyclohexylgroup;R²⁶ is H, a C₁-C₅alkyl group, a cyclopentyl or cyclohexyl group; andR²⁷ is H, a C₁-C₅alkyl group, a cyclopentyl or cyclohexyl group; withthe proviso that in case one of R²⁶ and R²⁷ is a cyclopentyl orcyclohexyl group, the other is H;R⁶ and R⁷ in formula (IIc) form together a ring

M, m, L, o, R¹, R², R³, R^(3′), R^(3″), R⁴, R^(4′), R⁵ and R⁶⁵ are asdefined above.

Preferably, R⁶ is a C₁-C₅alkyl group, or a C₃-C₆cycloalkyl group.

Depending on its preparation the metal carbene complex of formula

can be present as a mixture of different isomeric forms:

Formula (IIa) is an idealized or simplified manner of representation andshall comprise all isomeric forms.

In a preferred embodiment R is a group of formula

whereinR¹ and R² are independently of each other a C₁-C₅alkyl group, acyclopentyl or cyclohexyl group;R³ is H, a C₁-C₄alkyl group, a group of formula

whereinR¹⁰ is H, or a C₁-C₅alkyl group,R¹¹ is H, or a C₁-C₅alkyl group,R¹² is a C₁-C₅alkyl group, andR^(12′) is a C₁-C₅alkyl group.

In another preferred embodiment R is a group of formula

wherein

-   R² is CF₃, a C₁-C₅alkyl group, a cyclopentyl or cyclohexyl group;-   R³ is H, a C₁-C₅alkyl group, a cyclopentyl or cyclohexyl group; and-   R^(3′) is H, a C₁-C₅alkyl group, a cyclopentyl or cyclohexyl group,    with the proviso that in case one of R³ and R^(3′) is a cyclopentyl    or cyclohexyl group, the other is H.

In another preferred embodiment R is a group of formula

wherein

-   R³ is H, or a C₁-C₅alkyl group, and-   R^(3′) is H, especially a C₁-C₅alkyl group, a cyclopentyl or    cyclohexyl group, and-   R^(3″) is H, especially a C₁-C₅alkyl group, a cyclopentyl or    cyclohexyl group, with the proviso that if R^(3′) and R^(3″) are    different from H, then R³ is H.-   In another preferred embodiment R^(4′) is H; R⁴ is H, or a    C₁-C₅alkyl group; and R⁵ is H, or a C₁-C₅alkyl group.-   In another preferred embodiment R⁴ is H, or a C₁-C₅alkyl group, R⁵    is H, or a C₁-C₅alkyl group, R^(4′) is a group of formula

-    wherein-   R²⁰ is H, or a C₁-C₅alkyl group,-   R²¹ is H, or a C₁-C₅alkyl group,-   R²² is a C₁-C₅alkyl group, and-   R^(22′) is a C₁-C₅alkyl group.-   In another preferred embodiment R⁴ is H; R⁵ is H; and R^(4′) is a    group of formula

-    wherein R²² and R^(22′) are as defined above.-   In another preferred embodiment R⁴ is H; R^(4′) is H, or a    C₁-C₅alkyl group; and R⁵ is C₁-C₅alkyl group.-   In another preferred embodiment R⁴ and R^(4′) are H; and R⁵ is a    group of formula

-    wherein    R²⁰ is H, or a C₁-C₅alkyl group,    R²¹ is H, or a C₁-C₅alkyl group,    R²² is a C₁-C₅alkyl group, and    R^(22′) is a C₁-C₅alkyl group.    R⁶ and R⁷ are preferably independently of each other hydrogen, a    C₁-C₈alkyl group, especially ethyl, isopropyl, isobutyl, or    tert-butyl; a C₃-C₆cycloalkyl group, especially cyclopentyl, or    cyclohexyl; or R⁶ and R⁷ form together a ring

with the proviso that if one of R⁶ and R⁷ is a C₃-C₆cycloalkyl group,the other is H.

L is preferably a group (X-1), (X-2), (X-3), (X-4), (X-5), (X-6), (X-7),(X-8), (X-9), (X-10), (X-11), (X-12), (X-13), (X-14), (X-15), (X-16),(X-17), (X-18), (X-19), (X-20), (X-21), (X-22), (X-23), (X-24), (X-25),(X-26), or (X-27); more preferably a group (X-1), (X-2), (X-3), or(X-4). In case M is Ir and L is a group (X-5) to (X-27), o is preferably2 and m is preferably 1.

In a preferred embodiment the present invention is directed tometal-carbenes of formula

whereinR¹ and R² are independently of each other a C₁-C₅alkyl group, especiallymethyl, ethyl, iso-propyl, isobutyl and neopentyl; a cyclopentyl orcyclohexyl group,R³ is H, a C₁-C₄alkyl group, especially methyl, isopropyl, a group offormula

whereinR¹⁰ is H, or a C₁-C₅alkyl group,R¹¹ is H, or a C₁-C₅alkyl group, especially methyl, or isopropyl;R¹² is a C₁-C₅alkyl group, especially methyl, or isopropyl; andR^(12′) is a C₁-C₅alkyl group, especially methyl, or isopropyl;

whereinR² is CF₃, a C₁-C₅alkyl group, a cyclopentyl or cyclohexyl group;R³ is H, a C₁-C₅alkyl group, a cyclopentyl or cyclohexyl group; andR^(3′) is H, a C₁-C₅alkyl group, a cyclopentyl or cyclohexyl group; withthe proviso that in case one of R³ and R^(3′) is a cyclopentyl orcyclohexyl group, the other is H; or

whereinR³ is H, a C₁-C₅alkyl group, a cyclopentyl, or cyclohexyl group;R^(3′) is H, especially a C₁-C₅alkyl group, a cyclopentyl or cyclohexylgroup, andR^(3″) is H, especially a C₁-C₅alkyl group, a cyclopentyl or cyclohexylgroup;with the proviso that in case one of R³ and R^(3′) is a cyclopentyl orcyclohexyl group, the other is H;and with the further proviso that in case one of R^(3″) and R³ is acyclopentyl or a cyclohexyl group, the other is H;o is 1, or 2; m is 1, or 2; the sum of m+o is 3;L is a group of formula (X-1), (X-2), (X-3), (X-4), (X-5), (X-6), (X-7),(X-8), (X-9), (X-10), (X-11), (X-12), (X-13), (X-14), (X-15), (X-16),(X-17), (X-18), (X-19), (X-20), (X-21), (X-22), (X-23), (X-24), (X-25),(X-26), or (X-27) as defined above, more preferably a group (X-1),(X-2), (X-3), or (X-4); R⁴ and R⁵are independently of each other H, or aC₁-C₅alkyl group, especially methyl, ethyl, iso-propyl, or isobutyl,tert-butyl, or sec-butyl; a cyclopentyl or cyclohexyl group; andR⁶ and R⁷ are independently of each other hydrogen, a C₁-C₈alkyl group,a C₃-C₆cycloalkyl group; orR⁶ and R⁷ form together a ring

with the proviso that if one of R⁶ and R⁷ is a C₃-C₆cycloalkyl group,the other is H.

In case M is Ir and L is a group (X-5) to (X-27), o is preferably 2 andm is preferably 1. In case M is Ir and L is a group (X-1) to (X-4), o ispreferably 1 and m is preferably 2.

In said embodiment metal-carbene complexes of formula

are preferred, wherein L is a group (X-1) to (X-4) and the othersubstituents are as defined above.

In another preferred embodiment the present invention is directed tometal-carbene complexes of formula

whereinR¹ and R² are independently of each other a C₁-C₅alkyl group, especiallymethyl, ethyl, iso-propyl and isobutyl; a cyclopentyl or cyclohexylgroup,R³ is H, a C₁-C₄alkyl group, especially methyl, isopropyl, a group offormula

whereinR¹⁰ is H, or a C₁-C₅alkyl group, especially methyl, or isopropyl;R¹¹ is a C₁-C₅alkyl group, especially methyl, or isopropyl;R¹² is a C₁-C₅alkyl group, especially methyl, or isopropyl;R^(12′) is a C₁-C₅alkyl group, especially methyl, or isopropyl;

whereinR² is CF₃, a C₁-C₅alkyl group, a cyclopentyl or cyclohexyl group;R³ is H, a C₁-C₅alkyl group, a cyclopentyl or cyclohexyl group; andR^(3′) is H, a C₁-C₅alkyl group, a cyclopentyl or cyclohexyl group; withthe proviso that in case one of R³ and R^(3′) is a cyclopentyl orcyclohexyl group, the other is H; or

whereinR³ is H, or a C₁-C₅alkyl group, andR^(3′) is H, especially a C₁-C₅alkyl group, a cyclopentyl or cyclohexylgroup, andR^(3″) is H, especially a C₁-C₅alkyl group, a cyclopentyl or cyclohexylgroup; with the proviso that in case one of R³ and R^(3′) is acyclopentyl or cyclohexyl group, the other is H; and with the furtherproviso that in case one of R^(3″) and R³ is a cyclopentyl or acyclohexyl group, the other is H; andR⁴ and R⁵ are independently of each other H, or a C₁-C₅alkyl group,especially methyl, ethyl, iso-propyl, or isobutyl, tert-butyl, orsec-butyl; a cyclopentyl or cyclohexyl group; andR⁶ and R⁷ are independently of each other hydrogen, a C₁-C₈alkyl group,a C₃-C₆cycloalkyl group; orR⁶ and R⁷ form together a ring

with the proviso that if one of R⁶ and R⁷ is a C₃-C₆cycloalkyl group,the other is H.

Compounds of formula (IIIa), (IIIb), (IIId) and (IIIe) are morepreferred than compounds of formula (IIIc) and (IIIf). Compounds offormula (IIIa′) and (IIIb′) are more preferred than compounds of formula(IIIc′).

In a particularly preferred embodiment the present invention is directedto metal-carbene complexes of formula

especially

whereinR¹ and R² are independently of each other a C₁-C₅alkyl group, especiallymethyl, ethyl, iso-propyl, isobutyl and neopentyl; a cyclopentyl orcyclohexyl group,R³ is H, or a C₁-C₄alkyl group;

especially

whereinR² is CF₃, especially a C₁-C₅alkyl group, especially methyl, ethyl,iso-propyl and isobutyl; a cyclopentyl or cyclohexyl group;R³ is H, a C₁-C₅alkyl group, especially methyl, ethyl, iso-propyl andisobutyl; a cyclopentyl or cyclohexyl group; andR^(3′) is H, a C₁-C₅alkyl group, especially methyl, ethyl, iso-propyland isobutyl; a cyclopentyl or cyclohexyl group; with the proviso thatin case one of R³ and R^(3′) is a cyclopentyl or cyclohexyl group, theother is H; or

especially

whereinR³ is H, or a C₁-C₅alkyl group, especially methyl, ethyl, iso-propyl andisobutyl;R^(3′) is H, or a C₁-C₅alkyl group, especially methyl, ethyl, iso-propyland isobutyl; andR^(3″) is H, or a C₁-C₅alkyl group, especially methyl, ethyl, iso-propyland isobutyl; with the proviso that if R^(3′) and R^(3″) are differentfrom H, then R³ is H;L is a group (X-1), (X-2), (X-3), (X-4), (X-5), (X-6), (X-7), (X-8),(X-9), (X-10), (X-11), (X-12), (X-13), (X-14), (X-15), (X-16), (X-17),(X-18), (X-19), (X-20), (X-21), (X-22), (X-23), (X-24), (X-25), (X-26),or (X-27), especially (X-1), (X-2), (X-3), or (X-4), very especially(X-4); andR⁴ and R⁵ are independently of each other H, or a C₁-C₅alkyl group,especially methyl, ethyl, iso-propyl, or isobutyl, andR⁶ and R⁷ are independently of each other hydrogen, a C₁-C₈alkyl group,a C₃-C₆cycloalkyl group; orR⁶ and R⁷ form together a ring

with the proviso that if one of R⁶ and R⁷ is a a C₁-C₈alkyl group, orC₃-C₆cycloalkyl group, the other is H.

In another particularly preferred embodiment the present invention isdirected to metal-carbene complexes of formula

especially

whereinR¹ and R² are independently of each other a C₁-C₅alkyl group, especiallymethyl, ethyl, iso-propyl, isobutyl and neopentyl; a cyclopentyl orcyclohexyl group,R³ is H, or a C₁-C₄alkyl group;

especially

whereinR² is CF₃, especially a C₁-C₅alkyl group, especially methyl, ethyl,iso-propyl and isobutyl; a cyclopentyl or cyclohexyl group;R³ is H, a C₁-C₅alkyl group, especially methyl, ethyl, iso-propyl andisobutyl; a cyclopentyl or cyclohexyl group; andR^(3′) is H, a C₁-C₅alkyl group, especially methyl, ethyl, iso-propyland isobutyl; a cyclopentyl or cyclohexyl group; with the proviso thatin case one of R³ and R^(3′) is a cyclopentyl or cyclohexyl group, theother is H; or

especially

whereinR³ is H, or a C₁-C₅alkyl group, especially methyl, ethyl, iso-propyl andisobutyl;R^(3′) is H, or a C₁-C₅alkyl group, especially methyl, ethyl, iso-propyland isobutyl; andR^(3″) is H, or a C₁-C₅alkyl group, especially methyl, ethyl, iso-propyland isobutyl; with the proviso that if R^(3′) and R^(3″) are differentfrom H, then R³ is H; andR⁴ and R⁵ are independently of each other H, or a C₁-C₅alkyl group,especially methyl, ethyl, iso-propyl, or isobutyl, andR⁶ and R⁷ are independently of each other hydrogen, a C₁-C₈alkyl group,a C₃-C₆cycloalkyl group; orR⁶ and R⁷ form together a ring

with the proviso that if one of R⁶ and R⁷ is a C₁-C₈alkyl group, or aC₃-C₆cycloalkyl group, the other is H. R⁴ and R⁵ are preferably H.

Metal-carbene complexes of formula (IIId-1) and (IIIe-1) are morepreferred than metal-carbene complexes of formula

respectively. R⁶ is in the metal-carbene complexes of formula (IIId-2)and (IIIe-2) a C₁-C₈alkyl group, or a C₃-C₆cycloalkyl group, especiallya C₁-C₈alkyl group. R¹, R², R³, R^(3′). R⁴ and R⁵ are as defined above.

For example, the metal-carbene complex of formula

can be present as a mixture of different isomeric forms:

Formula (IIId-2) is an idealized or simplified manner of representationand shall comprise all isomeric forms. R⁴ and R⁵ are preferably H.

Examples of metal carbene-complexes are shown below:

Cpd. R¹ R² R³ R⁴ = R⁵ A-1 —CH₃ —CH₃ H H A-2 —CH₂CH₃ —CH₂CH₃ H H A-3iso-propyl iso-propyl H H A-4 iso-butyl iso-butyl H H A-5 neopentylneopentyl H H A-6 —CH₃ —CH₂CH₃ H H A-7

H H A-8

H H A-9 —CH₃ —CH₃ —CH₃ H A-10 ethyl ethyl —CH₃ H A-11 iso-propyliso-propyl —CH₃ H A-12 —CH₃ —CH₃ iso-propyl H A-13 ethyl ethyliso-propyl H A-14 iso-propyl iso-propyl iso-propyl H A-15 —CH₃ —CH₃ H—CH₃ A-16 —CH₂CH₃ —CH₂CH₃ H —CH₃ A-17 iso-propyl iso-propyl H —CH₃ A-18iso-butyl iso-butyl H —CH₃ A-19 neopentyl neopentyl H —CH₃ A-20 —CH₃—CH₂CH₃ H —CH₃ A-21

H —CH₃ A-22

H —CH₃ A-23 —CH₃ —CH₃ —CH₃ —CH₃ A-24 ethyl ethyl —CH₃ —CH₃ A-25iso-propyl iso-propyl —CH₃ —CH₃ A-26 —CH₃ —CH₃ iso-propyl —CH₃ A-27ethyl ethyl iso-propyl  CH₃ A-28 iso-propyl iso-propyl iso-propyl —CH₃A-29 —CH₃ —CH₃ H —CH₂CH₃ A-30 —CH₂CH₃ —CH₂CH₃ H —CH₂CH₃ A-31 iso-propyliso-propyl H —CH₂CH₃ A-32 iso-butyl iso-butyl H —CH₂CH₃ A-33 —CH₃—CH₂CH₃ H —CH₂CH₃ A-34 neopentyl neopentyl H —CH₂CH₃ A-35

H —CH₂CH₃ A-36

H —CH₂CH₃ A-37 —CH₃ —CH₃ —CH₃ —CH₂CH₃ A-38 ethyl ethyl —CH₃  CH₂CH₃ A-39iso-propyl iso-propyl —CH₃ —CH₂CH₃ A-40 —CH₃ —CH₃ iso-propyl —CH₂CH₃A-41 ethyl ethyl iso-propyl —CH₂CH₃ A-42 iso-propyl iso-propyliso-propyl —CH₂CH₃ A-43 —CH₃ —CH₃ H iso-propyl A-44 —CH₂CH₃ —CH₂CH₃ Hiso-propyl A-45 iso-propyl iso-propyl H iso-propyl A-46 iso-butyliso-butyl H iso-propyl A-47 neopentyl neopentyl H iso-propyl A-48 —CH₃—CH₂CH₃ H iso-propyl A-49

H iso-propyl A-50

H iso-propyl A-51 —CH₃ —CH₃ —CH₃ iso-propyl A-52 ethyl ethyl —CH₃iso-propyl A-53 iso-propyl iso-propyl —CH₃ iso-propyl A-54 —CH₃ —CH₃iso-propyl iso-propyl A-55 ethyl ethyl iso-propyl iso-propyl A-56iso-propyl iso-propyl iso-propyl iso-propyl A-57 —CH₃ —CH₃ H iso-butylA-58 —CH₂CH₃ —CH₂CH₃ H iso-butyl A-59 iso-propyl iso-propyl H iso-butylA-60 iso-butyl iso-butyl H iso-butyl A-61 neopentyl neopentyl Hiso-butyl A-62 —CH₃ —CH₂CH₃ H iso-butyl A-63

H iso-butyl A-64

H iso-butyl A-65 —CH₃ —CH₃ —CH₃ iso-butyl A-66 ethyl ethyl —CH₃iso-butyl A-67 iso-propyl iso-propyl —CH₃ iso-butyl A-68 —CH₃ —CH₃iso-propyl iso-butyl A-69 ethyl ethyl iso-propyl iso-butyl A-70iso-propyl iso-propyl iso-propyl iso-butyl A-71 —CH₃ —CH₃ H tert-butylA-72 —CH₂CH₃ —CH₂CH₃ H tert-butyl A-73 iso-propyl iso-propyl Htert-butyl A-74 iso-butyl iso-butyl H tert-butyl A-75 neopentylneopentyl H tert-butyl A-76 —CH₃ —CH₂CH₃ H tert-butyl A-77

H tert-butyl A-78

H tert-butyl A-79 —CH₃ —CH₃ —CH₃ tert-butyl A-80 ethyl ethyl —CH₃tert-butyl A-81 iso-propyl iso-propyl —CH₃ tert-butyl A-82 —CH₃ —CH₃iso-propyl tert-butyl A-83 ethyl ethyl iso-propyl tert-butyl A-84iso-propyl iso-propyl iso-propyl tert-butyl

Cpd. R¹ R² R³ R⁴ = R⁵ A′-1 —CH₃ —CH₃ H H A′-2 —CH₂CH₃ —CH₂CH₃ H H A′-3iso-propyl iso-propyl H H A′-4 iso-butyl iso-butyl H H A′-5 neopentylneopentyl H H A′-6 —CH₃ —CH₂CH₃ H H A′-7

H H A′-8

H H A′-9 —CH₃ —CH₃ —CH₃ H A′-10 ethyl ethyl —CH₃ H A′-11 iso-propyliso-propyl —CH₃ H A′-12 —CH₃ —CH₃ iso-propyl H A′-13 ethyl ethyliso-propyl H A′-14 iso-propyl iso-propyl iso-propyl H A′-15 —CH₃ —CH₃ H—CH₃ A′-16 —CH₂CH₃ —CH₂CH₃ H —CH₃ A′-17 iso-propyl iso-propyl H —CH₃A′-18 iso-butyl iso-butyl H —CH₃ A′-19 neopentyl neopentyl H —CH₃ A′-20—CH₃ —CH₂CH₃ H —CH₃ A′-21

H —CH₃ A′-22

H —CH₃ A′-23 —CH₃ —CH₃ —CH₃ —CH₃ A′-24 ethyl ethyl —CH₃ —CH₃ A′-25iso-propyl iso-propyl —CH₃ —CH₃ A′-26 —CH₃ —CH₃ iso-propyl —CH₃ A′-27ethyl ethyl iso-propyl —CH₃ A′-28 iso-propyl iso-propyl iso-propyl —CH₃A′-29 —CH₃ —CH₃ H —CH₂CH₃ A′-30 —CH₂CH₃ —CH₂CH₃ H —CH₂CH₃ A′-31iso-propyl iso-propyl H —CH₂CH₃ A′-32 iso-butyl iso-butyl H —CH₂CH₃A′-33 —CH₃ —CH₂CH₃ H —CH₂CH₃ A′-34 neopentyl neopentyl H —CH₂CH₃ A′-35

H —CH₂CH₃ A′-36

H —CH₂CH₃ A′-37 —CH₃ —CH₃ —CH₃ —CH₂CH₃ A′-38 ethyl ethyl —CH₃ —CH₂CH₃A′-39 iso-propyl iso-propyl —CH₃ —CH₂CH₃ A′-40 —CH₃ —CH₃ iso-propyl—CH₂CH₃ A′-41 ethyl ethyl iso-propyl —CH₂CH₃ A′-42 iso-propyl iso-propyliso-propyl —CH₂CH₃ A′-43 —CH₃ —CH₃ H iso-propyl A′-44 —CH₂CH₃ —CH₂CH₃ Hiso-propyl A′-45 iso-propyl iso-propyl H iso-propyl A′-46 iso-butyliso-butyl H iso-propyl A′-47 neopentyl neopentyl H iso-propyl A′-48 —CH₃—CH₂CH₃ H iso-propyl A′-49

H iso-propyl A′-50

H iso-propyl A′-51 —CH₃ —CH₃ —CH₃ iso-propyl A′-52 ethyl ethyl —CH₃iso-propyl A′-53 iso-propyl iso-propyl —CH₃ iso-propyl A′-54 —CH₃ —CH₃iso-propyl iso-propyl A′-55 ethyl ethyl iso-propyl iso-propyl A′-56iso-propyl iso-propyl iso-propyl iso-propyl A′-57 —CH₃ —CH₃ H iso-butylA′-58 —CH₂CH₃ —CH₂CH₃ H iso-butyl A′-59 iso-propyl iso-propyl Hiso-butyl A′-60 iso-butyl iso-butyl H iso-butyl A′-61 neopentylneopentyl H iso-butyl A′-62 —CH₃ —CH₂CH₃ H iso-butyl A′-63

H iso-butyl A′-64

H iso-butyl A′-65 —CH₃ —CH₃ —CH₃ iso-butyl A′-66 ethyl ethyl —CH₃iso-butyl A′-67 iso-propyl iso-propyl —CH₃ iso-butyl A′-68 —CH₃ —CH₃iso-propyl iso-butyl A′-69 ethyl ethyl iso-propyl iso-butyl A′-70iso-propyl iso-propyl iso-propyl iso-butyl

Cpd. R¹ R² R³ R⁴ = R⁵ B-1 —CH₃ —CH₃ H H B-2 —CH₂CH₃ —CH₂CH₃ H H B-3iso-propyl iso-propyl H H B-4 iso-butyl iso-butyl H H B-5 neopentylneopentyl H H B-6 —CH₃ —CH₂CH₃ H H B-7

H H B-8

H H B-9 —CH₃ —CH₃ —CH₃ H B-10 ethyl ethyl —CH₃ H B-11 iso-propyliso-propyl —CH₃ H B-12 —CH₃ —CH₃ iso-propyl H B-13 ethyl ethyliso-propyl H B-14 iso-propyl iso-propyl iso-propyl H B-15 —CH₃ —CH₃ H—CH₃ B-16 —CH₂CH₃ —CH₂CH₃ H —CH₃ B-17 iso-propyl iso-propyl H —CH₃ B-18iso-butyl iso-butyl H —CH₃ B-19 neopentyl neopentyl H —CH₃ B-20 —CH₃—CH₂CH₃ H —CH₃ B-21

H —CH₃ B-22

H —CH₃ B-23 —CH₃ —CH₃ —CH₃ —CH₃ B-24 ethyl ethyl —CH₃ —CH₃ B-25iso-propyl iso-propyl —CH₃ —CH₃ B-26 —CH₃ —CH₃ iso-propyl —CH₃ B-27ethyl ethyl iso-propyl —CH₃ B-28 iso-propyl iso-propyl iso-propyl —CH₃B-29 —CH₃ —CH₃ H —CH₂CH₃ B-30 —CH₂CH₃ —CH₂CH₃ H —CH₂CH₃ B-31 iso-propyliso-propyl H —CH₂CH₃ B-32 iso-butyl iso-butyl H —CH₂CH₃ B-33 —CH₃—CH₂CH₃ H —CH₂CH₃ B-34 neopentyl neopentyl H —CH₂CH₃ B-35

H —CH₂CH₃ B-36

H —CH₂CH₃ B-37 —CH₃ —CH₃ —CH₃ —CH₂CH₃ B-38 ethyl ethyl —CH₃ —CH₂CH₃ B-39iso-propyl iso-propyl —CH₃ —CH₂CH₃ B-40 —CH₃ —CH₃ iso-propyl —CH₂CH₃B-41 ethyl ethyl iso-propyl —CH₂CH₃ B-42 iso-propyl iso-propyliso-propyl —CH₂CH₃ B-43 —CH₃ —CH₃ H iso-propyl B-44 —CH₂CH₃ —CH₂CH₃ Hiso-propyl B-45 iso-propyl iso-propyl H iso-propyl B-46 iso-butyliso-butyl H iso-propyl B-47 neopentyl neopentyl H iso-propyl B-48 —CH₃—CH₂CH₃ H iso-propyl B-49

H iso-propyl B-50

H iso-propyl B-51 —CH₃ —CH₃ —CH₃ iso-propyl B-52 ethyl ethyl —CH₃iso-propyl B-53 iso-propyl iso-propyl —CH₃ iso-propyl B-54 —CH₃ —CH₃iso-propyl iso-propyl B-55 ethyl ethyl iso-propyl iso-propyl B-56iso-propyl iso-propyl iso-propyl iso-propyl B-57 —CH₃ —CH₃ H iso-butylB-58 —CH₂CH₃ —CH₂CH₃ H iso-butyl B-59 iso-propyl iso-propyl H iso-butylB-60 iso-butyl iso-butyl H iso-butyl B-61 neopentyl neopentyl Hiso-butyl B-62 —CH₃ —CH₂CH₃ H iso-butyl B-63

H iso-butyl B-64

H iso-butyl B-65 —CH₃ —CH₃ —CH₃ iso-butyl B-66 ethyl ethyl —CH₃iso-butyl B-67 iso-propyl iso-propyl —CH₃ iso-butyl B-68 —CH₃ —CH₃iso-propyl iso-butyl B-69 ethyl ethyl iso-propyl iso-butyl B-70iso-propyl iso-propyl iso-propyl iso-butyl B-71 —CH₃ —CH₃ H tert-butylB-72 —CH₂CH₃ —CH₂CH₃ H tert-butyl B-73 iso-propyl iso-propyl Htert-butyl B-74 iso-butyl iso-butyl H tert-butyl B-75 neopentylneopentyl H tert-butyl B-76 —CH₃ —CH₂CH₃ H tert-butyl B-77

H tert-butyl B-78

H tert-butyl B-79 —CH₃ —CH₃ —CH₃ tert-butyl B-80 ethyl ethyl —CH₃tert-butyl B-81 iso-propyl iso-propyl —CH₃ tert-butyl B-82 —CH₃ —CH₃iso-propyl tert-butyl B-83 ethyl ethyl iso-propyl tert-butyl B-84iso-propyl iso-propyl iso-propyl tert-butyl

Cpd. R¹ R² R³ R⁴ = R⁵ B′-1 —CH₃ —CH₃ H H B′-2 —CH₂CH₃ —CH₂CH₃ H H B′-3iso-propyl iso-propyl H H B′-4 iso-butyl iso-butyl H H B′-5 neopentylneopentyl H H B′-6 —CH₃ —CH₂CH₃ H H B′-7

H H B′-8

H H B′-9 —CH₃ —CH₃ —CH₃ H B′-10 ethyl ethyl —CH₃ H B′-11 iso-propyliso-propyl —CH₃ H B′-12 —CH₃ —CH₃ iso-propyl H B′-13 ethyl ethyliso-propyl H B′-14 iso-propyl iso-propyl iso-propyl H B′-15 —CH₃ —CH₃ H—CH₃ B′-16 —CH₂CH₃ —CH₂CH₃ H —CH₃ B′-17 iso-propyl iso-propyl H —CH₃B′-18 iso-butyl iso-butyl H —CH₃ B′-19 neopentyl neopentyl H —CH₃ B′-20—CH₃ —CH₂CH₃ H —CH₃ B′-21

H —CH₃ B′-22

H —CH₃ B′-23 —CH₃ —CH₃ —CH₃ —CH₃ B′-24 ethyl ethyl —CH₃ —CH₃ B′-25iso-propyl iso-propyl —CH₃ —CH₃ B′-26 —CH₃ —CH₃ iso-propyl —CH₃ B′-27ethyl ethyl iso-propyl —CH₃ B′-28 iso-propyl iso-propyl iso-propyl —CH₃B′-29 —CH₃ —CH₃ H —CH₂CH₃ B′-30 —CH₂CH₃ —CH₂CH₃ H —CH₂CH₃ B′-31iso-propyl iso-propyl H —CH₂CH₃ B′-32 iso-butyl iso-butyl H —CH₂CH₃B′-33 —CH₃ —CH₂CH₃ H —CH₂CH₃ B′-34 neopentyl neopentyl H —CH₂CH₃ B′-35

H —CH₂CH₃ B′-36

H —CH₂CH₃ B′-37 —CH₃ —CH₃ —CH₃ —CH₂CH₃ B′-38 ethyl ethyl —CH₃ —CH₂CH₃B′-39 iso-propyl iso-propyl —CH₃ —CH₂CH₃ B′-40 —CH₃ —CH₃ iso-propyl—CH₂CH₃ B′-41 ethyl ethyl iso-propyl —CH₂CH₃ B′-42 iso-propyl iso-propyliso-propyl —CH₂CH₃ B′-43 —CH₃ —CH₃ H iso-propyl B′-44 —CH₂CH₃ —CH₂CH₃ Hiso-propyl B′-45 iso-propyl iso-propyl H iso-propyl B′-46 iso-butyliso-butyl H iso-propyl B′-47 neopentyl neopentyl H iso-propyl B′-48 —CH₃—CH₂CH₃ H iso-propyl B′-49

H iso-propyl B′-50

H iso-propyl B′-51 —CH₃ —CH₃ —CH₃ iso-propyl B′-52 ethyl ethyl —CH₃iso-propyl B′-53 iso-propyl iso-propyl —CH₃ iso-propyl B′-54 —CH₃ —CH₃iso-propyl iso-propyl B′-55 ethyl ethyl iso-propyl iso-propyl B′-56iso-propyl iso-propyl iso-propyl iso-propyl B′-57 —CH₃ —CH₃ H iso-butylB′-58 —CH₂CH₃ —CH₂CH₃ H iso-butyl B′-59 iso-propyl iso-propyl Hiso-butyl B′-60 iso-butyl iso-butyl H iso-butyl B′-61 neopentylneopentyl H iso-butyl B′-62 —CH₃ —CH₂CH₃ H iso-butyl B′-63

H iso-butyl B′-64

H iso-butyl B′-65 —CH₃ —CH₃ —CH₃ iso-butyl B′-66 ethyl ethyl —CH₃iso-butyl B′-67 iso-propyl iso-propyl —CH₃ iso-butyl B′-68 —CH₃ —CH₃iso-propyl iso-butyl B′-69 ethyl ethyl iso-propyl iso-butyl B′-70iso-propyl iso-propyl iso-propyl iso-butyl

Cpd. R² R^(3′) R³ R⁴ = R⁵ C-1 —CH₃ —CH₃ H H C-2 —CH₂CH₃ —CH₂CH₃ H H C-3iso-propyl iso-propyl H H C-4 iso-butyl iso-butyl H H C-5

H H C-6

H H C-7 —CH₂CH₃ —CH₃ H H C-8 —CH₃ —CH₂CH₃ H H C-9 —CH₃ H —CH₃ H C-10—CH₂CH₃ H —CH₂CH₃ H C-11 iso-propyl H iso-propyl H C-12 iso-butyl Hiso-butyl H C-13

H

H C-14

H

H C-15 —CH₂CH₃ H —CH₃ H C-16 —CH₃ H —CH₂CH₃ H C-17 —CH₃ —CH₃ —CH₃ H C-18—CH₂CH₃ —CH₃ —CH₃ H C-19 iso-propyl —CH₃ —CH₃ H C-20 iso-butyl —CH₃ —CH₃H C-21

—CH₃ —CH₃ H C-22

—CH₃ —CH₃ H C-23 —CH₃ —CH₃ H —CH₃ C-24 —CH₂CH₃ —CH₂CH₃ H —CH₃ C-25iso-propyl iso-propyl H —CH₃ C-26 iso-butyl iso-butyl H —CH₃ C-27

H —CH₃ C-28

H —CH₃ C-29 —CH₂CH₃ —CH₃ H —CH₃ C-30 —CH₃ —CH₂CH₃ H —CH₃ C-31 —CH₃ H—CH₃ —CH₃ C-32 —CH₂CH₃ H —CH₂CH₃ —CH₃ C-33 iso-propyl H iso-propyl —CH₃C-34 iso-butyl H iso-butyl —CH₃ C-35

H

—CH₃ C-36

H

—CH₃ C-37 —CH₂CH₃ H —CH₃ —CH₃ C-38 —CH₃ H —CH₂CH₃ —CH₃ C-39 —CH₃ —CH₃—CH₃ —CH₃ C-40 —CH₂CH₃ —CH₃ —CH₃ —CH₃ C-41 iso-propyl —CH₃ —CH₃ —CH₃C-42 iso-butyl —CH₃ —CH₃ —CH₃ C-43

—CH₃ —CH₃ —CH₃ C-44

—CH₃ —CH₃ —CH₃ C-45 —CH₃ —CH₃ H —CH₂CH₃ C-46 —CH₂CH₃ —CH₂CH₃ H —CH₂CH₃C-47 iso-propyl iso-propyl H —CH₂CH₃ C-48 iso-butyl iso-butyl H —CH₂CH₃C-49

H —CH₂CH₃ C-50

H —CH₂CH₃ C-51 —CH₂CH₃ —CH₃ H —CH₂CH₃ C-52 —CH₃ —CH₂CH₃ H —CH₂CH₃ C-53—CH₃ H —CH₃ —CH₂CH₃ C-54 —CH₂CH₃ H —CH₂CH₃ —CH₂CH₃ C-55 iso-propyl Hiso-propyl —CH₂CH₃ C-56 iso-butyl H iso-butyl —CH₂CH₃ C-57

H

—CH₂CH₃ C-58

H

—CH₂CH₃ C-59 —CH₂CH₃ H —CH₃ —CH₂CH₃ C-60 —CH₃ H —CH₂CH₃ —CH₂CH₃ C-61—CH₃ —CH₃ —CH₃ —CH₂CH₃ C-62 —CH₂CH₃ —CH₃ —CH₃ —CH₂CH₃ C-63 iso-propyl—CH₃ —CH₃ —CH₂CH₃ C-64 iso-butyl —CH₃ —CH₃ —CH₂CH₃ C-65

—CH₃ —CH₃ —CH₂CH₃ C-66

—CH₃ —CH₃ —CH₂CH₃ C-67 —CH₃ —CH₃ H iso-propyl C-68 —CH₂CH₃ —CH₂CH₃ Hiso-propyl C-69 iso-propyl iso-propyl H iso-propyl C-70 iso-butyliso-butyl H iso-propyl C-71

H iso-propyl C-72

H iso-propyl C-73 —CH₂CH₃ —CH₃ H iso-propyl C-74 —CH₃ —CH₂CH₃ Hiso-propyl C-75 —CH₃ H —CH₃ iso-propyl C-76 —CH₂CH₃ H —CH₂CH₃ iso-propylC-77 iso-propyl H iso-propyl iso-propyl C-78 iso-butyl H iso-butyliso-propyl C-79

H

iso-propyl C-80

H

iso-propyl C-81 —CH₂CH₃ H —CH₃ iso-propyl C-82 —CH₃ H —CH₂CH₃ iso-propylC-83 —CH₃ —CH₃ —CH₃ iso-propyl C-84 —CH₂CH₃ —CH₃ —CH₃ iso-propyl C-85iso-propyl —CH₃ —CH₃ iso-propyl C-86 iso-butyl —CH₃ —CH₃ iso-propyl C-87

—CH₃ —CH₃ iso-propyl C-88

—CH₃ —CH₃ iso-propyl C-89 —CH₃ —CH₃ H iso-butyl C-90 —CH₂CH₃ —CH₂CH₃ Hiso-butyl C-91 iso-propyl iso-propyl H iso-butyl C-92 iso-butyliso-butyl H iso-butyl C-93

H iso-butyl C-94

H iso-butyl C-95 —CH₂CH₃ —CH₃ H iso-butyl C-96 —CH₃ —CH₂CH₃ H iso-butylC-97 —CH₃ H —CH₃ iso-butyl C-98 —CH₂CH₃ H —CH₂CH₃ iso-butyl C-99iso-propyl H iso-propyl iso-butyl C-100 iso-butyl H iso-butyl iso-butylC-101

H

iso-butyl C-102

H

iso-butyl C-103 —CH₂CH₃ H —CH₃ iso-butyl C-104 —CH₃ H —CH₂CH₃ iso-butylC-105 —CH₃ —CH₃ —CH₃ iso-butyl C-106 —CH₂CH₃ —CH₃ —CH₃ iso-butyl C-107iso-propyl —CH₃ —CH₃ iso-butyl C-108 iso-butyl —CH₃ —CH₃ iso-butyl C-109

—CH₃ —CH₃ iso-butyl C-110

—CH₃ —CH₃ iso-butyl C-111 —CH₃ —CH₃ H tert-butyl C-112 —CH₂CH₃ —CH₂CH₃ Htert-butyl C-113 iso-propyl iso-propyl H tert-butyl C-114 iso-butyliso-butyl H tert-butyl C-115 ethyl methyl H tert-butyl C-116 —CH₃—CH₂CH₃ H tert-butyl C-117

H tert-butyl C-118

H tert-butyl C-119 —CH₃ —CH₃ —CH₃ tert-butyl C-120 ethyl ethyl —CH₃tert-butyl C-121 iso-propyl iso-propyl —CH₃ tert-butyl C-122 —CH₃ —CH₃iso-propyl tert-butyl C-123 ethyl ethyl iso-propyl tert-butyl C-124iso-propyl iso-propyl iso-propyl tert-butyl C-125 —CH₃ H H H C-126—CH₂CH₃ H H H C-127 iso-propyl H H H C-128 iso-butyl H H H C-129

H H H C-130

H H H C-131 —CH₃ H H —CH₃ C-132 —CH₂CH₃ H H —CH₃ C-133 iso-propyl H H—CH₃ C-134 iso-butyl H H —CH₃ C-135

H H —CH₃ C-136

H H —CH₃ C-137 —CH₃ H H —CH₂CH₃ C-138 —CH₂CH₃ H H —CH₂CH₃ C-139iso-propyl H H —CH₂CH₃ C-140 iso-butyl H H —CH₂CH₃ C-141

H H —CH₂CH₃ C-142

H H —CH₂CH₃ C-143 —CH₃ H H iso-propyl C-144 —CH₂CH₃ H H iso-propyl C-145iso-propyl H H iso-propyl C-146 iso-butyl H H iso-propyl C-147

H H iso-propyl C-148

H H iso-propyl C-149 —CH₃ H H iso-butyl C-150 —CH₂CH₃ H H iso-butylC-151 iso-propyl H H iso-butyl C-152 iso-butyl H H iso-butyl C-153

H H iso-butyl C-154

H H iso-butyl C-155 —CH₃ H H tert-butyl C-156 —CH₂CH₃ H H tert-butylC-157 iso-propyl H H tert-butyl C-158 iso-butyl H H tert-butyl C-159

H H tert-butyl C-160

H H tert-butyl C-161 tert-butyl H H H C-162 2,2-dimethyl- H H H butanylC-163 3,3-dimethyl- H H H pentanyl

Cpd. R² R^(3′) R³ R⁴ = R⁵ C′-1 —CH₃ —CH₃ H H C′-2 —CH₂CH₃ —CH₂CH₃ H HC′-3 iso-propyl iso-propyl H H C′-4 iso-butyl iso-butyl H H C′-5

H H C′-6

H H C′-7 —CH₂CH₃ —CH₃ H H C′-8 —CH₃ —CH₂CH₃ H H C′-9 —CH₃ H —CH₃ H C′-10—CH₂CH₃ H —CH₂CH₃ H C′-11 iso-propyl H iso-propyl H C′-12 iso-butyl Hiso-butyl H C′-13

H

H C′-14

H

H C′-15 —CH₂CH₃ H —CH₃ H C′-16 —CH₃ H —CH₂CH₃ H C′-17 —CH₃ —CH₃ —CH₃ HC′-18 —CH₂CH₃ —CH₃ —CH₃ H C′-19 iso-propyl —CH₃ —CH₃ H C′-20 iso-butyl—CH₃ —CH₃ H C′-21

—CH₃ —CH₃ H C′-22

—CH₃ —CH₃ H C′-23 —CH₃ —CH₃ H —CH₃ C′-24 —CH₂CH₃ —CH₂CH₃ H —CH₃ C′-25iso-propyl iso-propyl H —CH₃ C′-26 iso-butyl iso-butyl H —CH₃ C′-27

H —CH₃ C′-28

H —CH₃ C′-29 —CH₂CH₃ —CH₃ H —CH₃ C′-30 —CH₃ —CH₂CH₃ H —CH₃ C′-31 —CH₃ H—CH₃ —CH₃ C′-32 —CH₂CH₃ H —CH₂CH₃ —CH₃ C′-33 iso-propyl H iso-propyl—CH₃ C′-34 iso-butyl H iso-butyl —CH₃ C′-35

H

—CH₃ C′-36

H

—CH₃ C′-37 —CH₂CH₃ H —CH₃ —CH₃ C′-38 —CH₃ H —CH₂CH₃ —CH₃ C′-39 —CH₃ —CH₃—CH₃ —CH₃ C′-40 —CH₂CH₃ —CH₃ —CH₃ —CH₃ C′-41 iso-propyl —CH₃ —CH₃ —CH₃C′-42 iso-butyl —CH₃ —CH₃ —CH₃ C′-43

—CH₃ —CH₃ —CH₃ C′-44

—CH₃ —CH₃ —CH₃ C′-45 —CH₃ —CH₃ H —CH₂CH₃ C′-46 —CH₂CH₃ —CH₂CH₃ H —CH₂CH₃C′-47 iso-propyl iso-propyl H —CH₂CH₃ C′-48 iso-butyl iso-butyl H—CH₂CH₃ C′-49

H —CH₂CH₃ C′-50

H —CH₂CH₃ C′-51 —CH₂CH₃ —CH₃ H —CH₂CH₃ C′-52 —CH₃ —CH₂CH₃ H —CH₂CH₃C′-53 —CH₃ H —CH₃ —CH₂CH₃ C′-54 —CH₂CH₃ H —CH₂CH₃ —CH₂CH₃ C′-55iso-propyl H iso-propyl —CH₂CH₃ C′-56 iso-butyl H iso-butyl —CH₂CH₃C′-57

H

—CH₂CH₃ C′-58

H

—CH₂CH₃ C′-59 —CH₂CH₃ H —CH₃ —CH₂CH₃ C′-60 —CH₃ H —CH₂CH₃ —CH₂CH₃ C′-61—CH₃ —CH₃ —CH₃ —CH₂CH₃ C′-62 —CH₂CH₃ —CH₃ —CH₃ —CH₂CH₃ C′-63 iso-propyl—CH₃ —CH₃ —CH₂CH₃ C′-64 iso-butyl —CH₃ —CH₃ —CH₂CH₃ C′-65

—CH₃ —CH₃ —CH₂CH₃ C′-66

—CH₃ —CH₃ —CH₂CH₃ C′-67 —CH₃ —CH₃ H iso-propyl C′-68 —CH₂CH₃ —CH₂CH₃ Hiso-propyl C′-69 iso-propyl iso-propyl H iso-propyl C′-70 iso-butyliso-butyl H iso-propyl C′-71

H iso-propyl C′-72

H iso-propyl C′-73 —CH₂CH₃ —CH₃ H iso-propyl C′-74 —CH₃ —CH₂CH₃ Hiso-propyl C′-75 —CH₃ H —CH₃ iso-propyl C′-76 —CH₂CH₃ H —CH₂CH₃iso-propyl C′-77 iso-propyl H iso-propyl iso-propyl C′-78 iso-butyl Hiso-butyl iso-propyl C′-79

H

iso-propyl C′-80

H

iso-propyl C′-81 —CH₂CH₃ H —CH₃ iso-propyl C′-82 —CH₃ H —CH₂CH₃iso-propyl C′-83 —CH₃ —CH₃ —CH₃ iso-propyl C′-84 —CH₂CH₃ —CH₃ —CH₃iso-propyl C′-85 iso-propyl —CH₃ —CH₃ iso-propyl C′-86 iso-butyl —CH₃—CH₃ iso-propyl C′-87

—CH₃ —CH₃ iso-propyl C′-88

—CH₃ —CH₃ iso-propyl C′-89 —CH₃ —CH₃ H iso-butyl C′-90 —CH₂CH₃ —CH₂CH₃ Hiso-butyl C′-91 iso-propyl iso-propyl H iso-butyl C′-92 iso-butyliso-butyl H iso-butyl C′-93

H iso-butyl C′-94

H iso-butyl C′-95 —CH₂CH₃ —CH₃ H iso-butyl C′-96 —CH₃ —CH₂CH₃ Hiso-butyl C′-97 —CH₃ H —CH₃ iso-butyl C′-98 —CH₂CH₃ H —CH₂CH₃ iso-butylC′-99 iso-propyl H iso-propyl iso-butyl C′-100 iso-butyl H iso-butyliso-butyl C′-101

H

iso-butyl C′-102

H

iso-butyl C′-103 —CH₂CH₃ H —CH₃ iso-butyl C′-104 —CH₃ H —CH₂CH₃iso-butyl C′-105 —CH₃ —CH₃ —CH₃ iso-butyl C′-106 —CH₂CH₃ —CH₃ —CH₃iso-butyl C′-107 iso-propyl —CH₃ —CH₃ iso-butyl C′-108 iso-butyl —CH₃—CH₃ iso-butyl C′-109

—CH₃ —CH₃ iso-butyl C′-110

—CH₃ —CH₃ iso-butyl C′-111 —CH₃ H H H C′-112 —CH₂CH₃ H H H C′-113iso-propyl H H H C′-114 iso-butyl H H H C′-115

H H H C′-116

H H H C′-117 —CH₃ H H —CH₃ C′-118 —CH₂CH₃ H H —CH₃ C′-119 iso-propyl H H—CH₃ C′-120 iso-butyl H H —CH₃ C′-121

H H —CH₃ C′-122

H H —CH₃ C′-123 —CH₃ H H —CH₂CH₃ C′-124 —CH₂CH₃ H H —CH₂CH₃ C′-125iso-propyl H H —CH₂CH₃ C′-126 iso-butyl H H —CH₂CH₃ C′-127

H H —CH₂CH₃ C′-128

H H —CH₂CH₃ C′-129 —CH₃ H H iso-propyl C′-130 —CH₂CH₃ H H iso-propylC′-131 iso-propyl H H iso-propyl C′-132 iso-butyl H H iso-propyl C′-133

H H iso-propyl C′-134

H H iso-propyl C′-135 —CH₃ H H iso-butyl C′-136 —CH₂CH₃ H H iso-butylC′-137 iso-propyl H H iso-butyl C′-138 iso-butyl H H iso-butyl C′-139

H H iso-butyl C′-140

H H iso-butyl C′-141 tert-butyl H H H C′-142 2,2-dimethyl- H H H butanylC′-143 3,3-dimethyl- H H H pentanyl

Cpd. R² R^(3′) R³ R⁴ = R⁵ D-1 —CH₃ —CH₃ H H D-2 —CH₂CH₃ —CH₂CH₃ H H D-3iso-propyl iso-propyl H H D-4 iso-butyl iso-butyl H H D-5

H H D-6

H H D-7 —CH₂CH₃ —CH₃ H H D-8 —CH₃ —CH₂CH₃ H H D-9 —CH₃ H —CH₃ H D-10—CH₂CH₃ H —CH₂CH₃ H D-11 iso-propyl H iso-propyl H D-12 iso-butyl Hiso-butyl H D-13

H

H D-14

H

H D-15 —CH₂CH₃ H —CH₃ H D-16 —CH₃ H —CH₂CH₃ H D-17 —CH₃ —CH₃ —CH₃ H D-18—CH₂CH₃ —CH₃ —CH₃ H D-19 iso-propyl —CH₃ —CH₃ H D-20 iso-butyl —CH₃ —CH₃H D-21

—CH₃ —CH₃ H D-22

—CH₃ —CH₃ H D-23 —CH₃ —CH₃ H —CH₃ D-24 —CH₂CH₃ —CH₂CH₃ H —CH₃ D-25iso-propyl iso-propyl H —CH₃ D-26 iso-butyl iso-butyl H —CH₃ D-27

H —CH₃ D-28

H —CH₃ D-29 —CH₂CH₃ —CH₃ H —CH₃ D-30 —CH₃ —CH₂CH₃ H —CH₃ D-31 —CH₃ H—CH₃ —CH₃ D-32 —CH₂CH₃ H —CH₂CH₃ —CH₃ D-33 iso-propyl H iso-propyl —CH₃D-34 iso-butyl H iso-butyl —CH₃ D-35

H

—CH₃ D-36

H

—CH₃ D-37 —CH₂CH₃ H —CH₃ —CH₃ D-38 —CH₃ H —CH₂CH₃ —CH₃ D-39 —CH₃ —CH₃—CH₃ —CH₃ D-40 —CH₂CH₃ —CH₃ —CH₃ —CH₃ D-41 iso-propyl —CH₃ —CH₃ —CH₃D-42 iso-butyl —CH₃ —CH₃ —CH₃ D-43

—CH₃ —CH₃ —CH₃ D-44

—CH₃ —CH₃ —CH₃ D-45 —CH₃ —CH₃ H —CH₂CH₃ D-46 —CH₂CH₃ —CH₂CH₃ H —CH₂CH₃D-47 iso-propyl iso-propyl H —CH₂CH₃ D-48 iso-butyl iso-butyl H —CH₂CH₃D-49

H —CH₂CH₃ D-50

H —CH₂CH₃ D-51 —CH₂CH₃ —CH₃ H —CH₂CH₃ D-52 —CH₃ —CH₂CH₃ H —CH₂CH₃ D-53—CH₃ H —CH₃ —CH₂CH₃ D-54 —CH₂CH₃ H —CH₂CH₃ —CH₂CH₃ D-55 iso-propyl Hiso-propyl —CH₂CH₃ D-56 iso-butyl H iso-butyl —CH₂CH₃ D-57

H

—CH₂CH₃ D-58

H

—CH₂CH₃ D-59 —CH₂CH₃ H —CH₃ —CH₂CH₃ D-60 —CH₃ H —CH₂CH₃ —CH₂CH₃ D-61—CH₃ —CH₃ —CH₃ —CH₂CH₃ D-62 —CH₂CH₃ —CH₃ —CH₃ —CH₂CH₃ D-63 iso-propyl—CH₃ —CH₃ —CH₂CH₃ D-64 iso-butyl —CH₃ —CH₃ —CH₂CH₃ D-65

—CH₃ —CH₃ —CH₂CH₃ D-66

—CH₃ —CH₃ —CH₂CH₃ D-67 —CH₃ —CH₃ H iso-propyl D-68 —CH₂CH₃ —CH₂CH₃ Hiso-propyl D-69 iso-propyl iso-propyl H iso-propyl D-70 iso-butyliso-butyl H iso-propyl D-71

H iso-propyl D-72

H iso-propyl D-73 —CH₂CH₃ —CH₃ H iso-propyl D-74 —CH₃ —CH₂CH₃ Hiso-propyl D-75 —CH₃ H —CH₃ iso-propyl D-76 —CH₂CH₃ H —CH₂CH₃ iso-propylD-77 iso-propyl H iso-propyl iso-propyl D-78 iso-butyl H iso-butyliso-propyl D-79

H

iso-propyl D-80

H

iso-propyl D-81 —CH₂CH₃ H —CH₃ iso-propyl D-82 —CH₃ H —CH₂CH₃ iso-propylD-83 —CH₃ —CH₃ —CH₃ iso-propyl D-84 —CH₂CH₃ —CH₃ —CH₃ iso-propyl D-85iso-propyl —CH₃ —CH₃ iso-propyl D-86 iso-butyl —CH₃ —CH₃ iso-propyl D-87

—CH₃ —CH₃ iso-propyl D-88

—CH₃ —CH₃ iso-propyl D-89 —CH₃ —CH₃ H iso-butyl D-90 —CH₂CH₃ —CH₂CH₃ Hiso-butyl D-91 iso-propyl iso-propyl H iso-butyl D-92 iso-butyliso-butyl H iso-butyl D-93

H iso-butyl D-94

H iso-butyl D-95 —CH₂CH₃ —CH₃ H iso-butyl D-96 —CH₃ —CH₂CH₃ H iso-butylD-97 —CH₃ H —CH₃ iso-butyl D-98 —CH₂CH₃ H —CH₂CH₃ iso-butyl D-99iso-propyl H iso-propyl iso-butyl D-100 iso-butyl H iso-butyl iso-butylD-101

H

iso-butyl D-102

H

iso-butyl D-103 —CH₂CH₃ H —CH₃ iso-butyl D-104 —CH₃ H —CH₂CH₃ iso-butylD-105 —CH₃ —CH₃ —CH₃ iso-butyl D-106 —CH₂CH₃ —CH₃ —CH₃ iso-butyl D-107iso-propyl —CH₃ —CH₃ iso-butyl D-108 iso-butyl —CH₃ —CH₃ iso-butyl D-109

—CH₃ —CH₃ iso-butyl D-110

—CH₃ —CH₃ iso-butyl D-111 —CH₃ —CH₃ H tert-butyl D-112 —CH₂CH₃ —CH₂CH₃ Htert-butyl D-113 iso-propyl iso-propyl H tert-butyl D-114 iso-butyliso-butyl H tert-butyl D-115 ethyl methyl H tert-butyl D-116 —CH₃—CH₂CH₃ H tert-butyl D-117

H tert-butyl D-118

H tert-butyl D-119 —CH₃ —CH₃ —CH₃ tert-butyl D-120 ethyl ethyl —CH₃tert-butyl D-121 iso-propyl iso-propyl —CH₃ tert-butyl D-122 —CH₃ —CH₃iso-propyl tert-butyl D-123 ethyl ethyl iso-propyl tert-butyl D-124iso-propyl iso-propyl iso-propyl tert-butyl D-125 —CH₃ H H H D-126—CH₂CH₃ H H H D-127 iso-propyl H H H D-128 iso-butyl H H H D-129

H H H D-130

H H H D-131 —CH₃ H H —CH₃ D-132 —CH₂CH₃ H H —CH₃ D-133 iso-propyl H H—CH₃ D-134 iso-butyl H H —CH₃ D-135

H H —CH₃ D-136

H H —CH₃ D-137 —CH₃ H H —CH₂CH₃ D-138 —CH₂CH₃ H H —CH₂CH₃ D-139iso-propyl H H —CH₂CH₃ D-140 iso-butyl H H —CH₂CH₃ D-141

H H —CH₂CH₃ D-142

H H —CH₂CH₃ D-143 —CH₃ H H iso-propyl D-144 —CH₂CH₃ H H iso-propyl D-145iso-propyl H H iso-propyl D-146 iso-butyl H H iso-propyl D-147

H H iso-propyl D-148

H H iso-propyl D-149 —CH₃ H H iso-butyl D-150 —CH₂CH₃ H H iso-butylD-151 iso-propyl H H iso-butyl D-152 iso-butyl H H iso-butyl D-153

H H iso-butyl D-154

H H iso-butyl D-155 —CH₃ H H tert-butyl D-156 —CH₂CH₃ H H tert-butylD-157 iso-propyl H H tert-butyl D-158 iso-butyl H H tert-butyl D-159

H H tert-butyl D-160

H H tert-butyl D-161 tert-butyl H H H D-162 2,2-dimethyl- H H H butanylD-163 3,3-dimethyl- H H H pentanyl

Cpd. R² R^(3′) R³ R⁴ = R⁵ D′-1 —CH₃ —CH₃ H H D′-2 —CH₂CH₃ —CH₂CH₃ H HD′-3 iso-propyl iso-propyl H H D′-4 iso-butyl iso-butyl H H D′-5

H H D′-6

H H D′-7 —CH₂CH₃ —CH₃ H H D′-8 —CH₃ —CH₂CH₃ H H D′-9 —CH₃ H —CH₃ H D′-10—CH₂CH₃ H —CH₂CH₃ H D′-11 iso-propyl H iso-propyl H D′-12 iso-butyl Hiso-butyl H D′-13

H

H D′-14

H

H D′-15 —CH₂CH₃ H —CH₃ H D′-16 —CH₃ H —CH₂CH₃ H D′-17 —CH₃ —CH₃ —CH₃ HD′-18 —CH₂CH₃ —CH₃ —CH₃ H D′-19 iso-propyl —CH₃ —CH₃ H D′-20 iso-butyl—CH₃ —CH₃ H D′-21

—CH₃ —CH₃ H D′-22

—CH₃ —CH₃ H D′-23 —CH₃ —CH₃ H —CH₃ D′-24 —CH₂CH₃ —CH₂CH₃ H —CH₃ D′-25iso-propyl iso-propyl H —CH₃ D′-26 iso-butyl iso-butyl H —CH₃ D′-27

H —CH₃ D′-28

H —CH₃ D′-29 —CH₂CH₃ —CH₃ H —CH₃ D′-30 —CH₃ —CH₂CH₃ H —CH₃ D′-31 —CH₃ H—CH₃ —CH₃ D′-32 —CH₂CH₃ H —CH₂CH₃ —CH₃ D′-33 iso-propyl H iso-propyl—CH₃ D′-34 iso-butyl H iso-butyl —CH₃ D′-35

H

—CH₃ D′-36

H

—CH₃ D′-37 —CH₂CH₃ H —CH₃ —CH₃ D′-38 —CH₃ H —CH₂CH₃ —CH₃ D′-39 —CH₃ —CH₃—CH₃ —CH₃ D′-40 —CH₂CH₃ —CH₃ —CH₃ —CH₃ D′-41 iso-propyl —CH₃ —CH₃ —CH₃D′-42 iso-butyl —CH₃ —CH₃ —CH₃ D′-43

—CH₃ —CH₃ —CH₃ D′-44

—CH₃ —CH₃ —CH₃ D′-45 —CH₃ —CH₃ H —CH₂CH₃ D′-46 —CH₂CH₃ —CH₂CH₃ H —CH₂CH₃D′-47 iso-propyl iso-propyl H —CH₂CH₃ D′-48 iso-butyl iso-butyl H—CH₂CH₃ D′-49

H —CH₂CH₃ D′-50

H —CH₂CH₃ D′-51 —CH₂CH₃ —CH₃ H —CH₂CH₃ D′-52 —CH₃ —CH₂CH₃ H —CH₂CH₃D′-53 —CH₃ H —CH₃ —CH₂CH₃ D′-54 —CH₂CH₃ H —CH₂CH₃ —CH₂CH₃ D′-55iso-propyl H iso-propyl —CH₂CH₃ D′-56 iso-butyl H iso-butyl —CH₂CH₃D′-57

H

—CH₂CH₃ D′-58

H

—CH₂CH₃ D′-59 —CH₂CH₃ H —CH₃ —CH₂CH₃ D′-60 —CH₃ H —CH₂CH₃ —CH₂CH₃ D′-61—CH₃ —CH₃ —CH₃ —CH₂CH₃ D′-62 —CH₂CH₃ —CH₃ —CH₃ —CH₂CH₃ D′-63 iso-propyl—CH₃ —CH₃ —CH₂CH₃ D′-64 iso-butyl —CH₃ —CH₃ —CH₂CH₃ D′-65

—CH₃ —CH₃ —CH₂CH₃ D′-66

—CH₃ —CH₃ —CH₂CH₃ D′-67 —CH₃ —CH₃ H iso-propyl D′-68 —CH₂CH₃ —CH₂CH₃ Hiso-propyl D′-69 iso-propyl iso-propyl H iso-propyl D′-70 iso-butyliso-butyl H iso-propyl D′-71

H iso-propyl D′-72

H iso-propyl D′-73 —CH₂CH₃ —CH₃ H iso-propyl D′-74 —CH₃ —CH₂CH₃ Hiso-propyl D′-75 —CH₃ H —CH₃ iso-propyl D′-76 —CH₂CH₃ H —CH₂CH₃iso-propyl D′-77 iso-propyl H iso-propyl iso-propyl D′-78 iso-butyl Hiso-butyl iso-propyl D′-79

H

iso-propyl D′-80

H

iso-propyl D′-81 —CH₂CH₃ H —CH₃ iso-propyl D′-82 —CH₃ H —CH₂CH₃iso-propyl D′-83 —CH₃ —CH₃ —CH₃ iso-propyl D′-84 —CH₂CH₃ —CH₃ —CH₃iso-propyl D′-85 iso-propyl —CH₃ —CH₃ iso-propyl D′-86 iso-butyl —CH₃—CH₃ iso-propyl D′-87

—CH₃ —CH₃ iso-propyl D′-88

—CH₃ —CH₃ iso-propyl D′-89 —CH₃ —CH₃ H iso-butyl D′-90 —CH₂CH₃ —CH₂CH₃ Hiso-butyl D′-91 iso-propyl iso-propyl H iso-butyl D′-92 iso-butyliso-butyl H iso-butyl D′-93

H iso-butyl D′-94

H iso-butyl D′-95 —CH₂CH₃ —CH₃ H iso-butyl D′-96 —CH₃ —CH₂CH₃ Hiso-butyl D′-97 —CH₃ H —CH₃ iso-butyl D′-98 —CH₂CH₃ H —CH₂CH₃ iso-butylD′-99 iso-propyl H iso-propyl iso-butyl D′-100 iso-butyl H iso-butyliso-butyl D′-101

H

iso-butyl D′-102

H

iso-butyl D′-103 —CH₂CH₃ H —CH₃ iso-butyl D′-104 —CH₃ H —CH₂CH₃iso-butyl D′-105 —CH₃ —CH₃ —CH₃ iso-butyl D′-106 —CH₂CH₃ —CH₃ —CH₃iso-butyl D′-107 iso-propyl —CH₃ —CH₃ iso-butyl D′-108 iso-butyl —CH₃—CH₃ iso-butyl D′-109

—CH₃ —CH₃ iso-butyl D′-110

—CH₃ —CH₃ iso-butyl D′-111 —CH₃ H H H D′-112 —CH₂CH₃ H H H D′-113iso-propyl H H H D′-114 iso-butyl H H H D′-115

H H H D′-116

H H H D′-117 —CH₃ H H —CH₃ D′-118 —CH₂CH₃ H H —CH₃ D′-119 iso-propyl H H—CH₃ D′-120 iso-butyl H H —CH₃ D′-121

H H —CH₃ D′-122

H H —CH₃ D′-123 —CH₃ H H —CH₂CH₃ D′-124 —CH₂CH₃ H H —CH₂CH₃ D′-125iso-propyl H H —CH₂CH₃ D′-126 iso-butyl H H —CH₂CH₃ D′-127

H H —CH₂CH₃ D′-128

H H —CH₂CH₃ D′-129 —CH₃ H H iso-propyl D′-130 —CH₂CH₃ H H iso-propylD′-131 iso-propyl H H iso-propyl D′-132 iso-butyl H H iso-propyl D′-133

H H iso-propyl D′-134

H H iso-propyl D′-135 —CH₃ H H iso-butyl D′-136 —CH₂CH₃ H H iso-butylD′-137 iso-propyl H H iso-butyl D′-138 iso-butyl H H iso-butyl D′-139

H H iso-butyl D′-140

H H iso-butyl D′-141 tert-butyl H H H D′-142 2,2-dimethyl- H H H butanylD′-143 3,3-dimethyl- H H H pentanyl

Cpd. R^(3′) R³ R^(3″) R⁴ = R⁵ E-1 —CH₃ H —CH₃ H E-2 —CH₂CH₃ H —CH₂CH₃ HE-3 iso-propyl H iso-propyl H E-4 iso-butyl H iso-butyl H E-5

H

H E-6

H

H E-7 —CH₂CH₃ H —CH₃ H E-8 —CH₃ H —CH₂CH₃ H E-9 —CH₃ —CH₃ H H E-10—CH₂CH₃ —CH₂CH₃ H H E-11 iso-butyl iso-butyl H H E-12 —CH₂CH₃ —CH₃ H HE-13 —CH₃ —CH₂CH₃ H H E-14 —CH₃ H —CH₃ —CH₂CH₃ E-15 —CH₂CH₃ H —CH₂CH₃—CH₂CH₃ E-16 iso-propyl H iso-propyl —CH₂CH₃ E-17 iso-butyl H iso-butyl—CH₂CH₃ E-18

H

—CH₂CH₃ E-19

H

—CH₂CH₃ E-20 —CH₂CH₃ H —CH₃ —CH₂CH₃ E-21 —CH₃ H —CH₂CH₃ —CH₂CH₃ E-22—CH₃ —CH₃ H —CH₂CH₃ E-23 —CH₂CH₃ —CH₂CH₃ H —CH₂CH₃ E-24 iso-butyliso-butyl H —CH₂CH₃ E-25 —CH₂CH₃ —CH₃ H —CH₂CH₃ E-26 —CH₃ —CH₂CH₃ H—CH₂CH₃ E-27 —CH₃ H —CH₃ iso-propyl E-28 —CH₂CH₃ H —CH₂CH₃ iso-propylE-29 iso-propyl H iso-propyl iso-propyl E-30 iso-butyl H iso-butyliso-propyl E-31

H

iso-propyl E-32

H

iso-propyl E-33 —CH₂CH₃ H —CH₃ iso-propyl E-34 —CH₃ H —CH₂CH₃ iso-propylE-35 —CH₃ —CH₃ H iso-propyl E-36 —CH₂CH₃ —CH₂CH₃ H iso-propyl E-37iso-butyl iso-butyl H iso-propyl E-38 —CH₂CH₃ —CH₃ H iso-propyl E-39—CH₃ —CH₂CH₃ H iso-propyl E-40 —CH₃ H —CH₃ iso-butyl E-41 —CH₂CH₃ H—CH₂CH₃ iso-butyl E-42 iso-propyl H iso-propyl iso-butyl E-43 iso-butylH iso-butyl iso-butyl E-44

H

iso-butyl E-45

H

iso-butyl E-46 —CH₂CH₃ H —CH₃ iso-butyl E-47 —CH₃ H —CH₂CH₃ iso-butylE-48 —CH₃ —CH₃ H iso-butyl E-49 —CH₂CH₃ —CH₂CH₃ H iso-butyl E-50iso-butyl iso-butyl H iso-butyl E-51 —CH₂CH₃ —CH₃ H iso-butyl E-52 —CH₃—CH₂CH₃ H iso-butyl E-53 —CH₃ —CH₃ H tert-butyl E-54 —CH₂CH₃ —CH₂CH₃ Htert-butyl E-55 iso-propyl iso-propyl H tert-butyl E-56 iso-butyliso-butyl H tert-butyl E-57 neopentyl neopentyl H tert-butyl E-58 —CH₃—CH₂CH₃ H tert-butyl E-59

H tert-butyl E-60

H tert-butyl E-61 —CH₃ —CH₃ —CH₃ tert-butyl E-62 ethyl ethyl —CH₃tert-butyl E-63 iso-propyl iso-propyl —CH₃ tert-butyl E-64 —CH₃ —CH₃iso-propyl tert-butyl E-65 ethyl ethyl iso-propyl tert-butyl E-66iso-propyl iso-propyl iso-propyl tert-butyl E-67 —CH₃ —CH₃ H tert-butylE-68 H H —CH₃ H E-69 H H —CH₂CH₃ H E-70 H H iso-propyl H E-71 H Hiso-butyl H E-72 H H

H E-73 H H

H E-74 H —CH₃ H H E-75 H —CH₃ H H E-76 H —CH₂CH₃ H H E-77 H iso-propyl HH E-78 H iso-butyl H H E-79 H

H H E-80 H

H H E-81 —CH₃ H —CH₃ —CH₃ E-82 —CH₂CH₃ H —CH₂CH₃ —CH₃ E-83 iso-propyl Hiso-propyl —CH₃ E-84 iso-butyl H iso-butyl —CH₃ E-85

H

—CH₃ E-86

H

—CH₃ E-87 —CH₂CH₃ H —CH₃ —CH₃ E-88 —CH₃ H —CH₂CH₃ —CH₃ E-89 —CH₃ —CH₃ H—CH₃ E-90 —CH₂CH₃ —CH₂CH₃ H —CH₃ E-91 iso-butyl iso-butyl H —CH₃ E-92—CH₂CH₃ —CH₃ H —CH₃ E-93 —CH₃ —CH₂CH₃ H —CH₃

Cpd. R^(3′) R³ R^(3″) R⁴ = R⁵ E′-1 —CH₃ H —CH₃ H E′-2 —CH₂CH₃ H —CH₂CH₃H E′-3 iso-propyl H iso-propyl H E′-4 iso-butyl H iso-butyl H E′-5

H

H E′-6

H

H E′-7 —CH₂CH₃ H —CH₃ H E′-8 —CH₃ H —CH₂CH₃ H E′-9 —CH₃ —CH₃ H H E′-10—CH₂CH₃ —CH₂CH₃ H H E′-11 iso-butyl iso-butyl H H E′-12 —CH₂CH₃ —CH₃ H HE′-13 —CH₃ —CH₂CH₃ H H E′-14 —CH₃ H —CH₃ —CH₂CH₃ E′-15 —CH₂CH₃ H —CH₂CH₃—CH₂CH₃ E′-16 iso-propyl H iso-propyl —CH₂CH₃ E′-17 iso-butyl Hiso-butyl —CH₂CH₃ E′-18

H

—CH₂CH₃ E′-19

H

—CH₂CH₃ E′-20 —CH₂CH₃ H —CH₃ —CH₂CH₃ E′-21 —CH₃ H —CH₂CH₃ —CH₂CH₃ E′-22—CH₃ —CH₃ H —CH₂CH₃ E′-23 —CH₂CH₃ —CH₂CH₃ H —CH₂CH₃ E′-24 iso-butyliso-butyl H —CH₂CH₃ E′-25 —CH₂CH₃ —CH₃ H —CH₂CH₃ E′-26 —CH₃ —CH₂CH₃ H—CH₂CH₃ E′-27 —CH₃ H —CH₃ iso-propyl E′-28 —CH₂CH₃ H —CH₂CH₃ iso-propylE′-29 iso-propyl H iso-propyl iso-propyl E′-30 iso-butyl H iso-butyliso-propyl E′-31

H

iso-propyl E′-32

H

iso-propyl E′-33 —CH₂CH₃ H —CH₃ iso-propyl E′-34 —CH₃ H —CH₂CH₃iso-propyl E′-35 —CH₃ —CH₃ H iso-propyl E′-36 —CH₂CH₃ —CH₂CH₃ Hiso-propyl E′-37 iso-butyl iso-butyl H iso-propyl E′-38 —CH₂CH₃ —CH₃ Hiso-propyl E′-39 —CH₃ —CH₂CH₃ H iso-propyl E′-40 —CH₃ H —CH₃ iso-butylE′-41 —CH₂CH₃ H —CH₂CH₃ iso-butyl E′-42 iso-propyl H iso-propyliso-butyl E′-43 iso-butyl H iso-butyl iso-butyl E′-44

H

iso-butyl E′-45

H

iso-butyl E′-46 —CH₂CH₃ H —CH₃ iso-butyl E′-47 —CH₃ H —CH₂CH₃ iso-butylE′-48 —CH₃ —CH₃ H iso-butyl E′-49 —CH₂CH₃ —CH₂CH₃ H iso-butyl E′-50iso-butyl iso-butyl H iso-butyl E′-51 —CH₂CH₃ —CH₃ H iso-butyl E′-52—CH₃ —CH₂CH₃ H iso-butyl E′-53 H H —CH₃ H E′-54 H H —CH₂CH₃ H E′-55 H Hiso-propyl H E′-56 H H iso-butyl H E′-57 H H

H E′-58 H H

H E′-59 H —CH₃ H H E′-60 H —CH₃ H H E′-61 H —CH₂CH₃ H H E′-62 Hiso-propyl H H E′-63 H iso-butyl H H E′-64 H

H H E′-65 H

H H E′-66 —CH₃ H —CH₃ —CH₃ E′-67 —CH₂CH₃ H —CH₂CH₃ —CH₃ E′-68 iso-propylH iso-propyl —CH₃ E′-69 iso-butyl H iso-butyl —CH₃ E′-70

H

—CH₃ E′-71

H

—CH₃ E′-72 —CH₂CH₃ H —CH₃ —CH₃ E′-73 —CH₃ H —CH₂CH₃ —CH₃ E′-74 —CH₃ —CH₃H —CH₃ E′-75 —CH₂CH₃ —CH₂CH₃ H —CH₃ E′-76 iso-butyl iso-butyl H —CH₃E′-77 —CH₂CH₃ —CH₃ H —CH₃ E′-78 —CH₃ —CH₂CH₃ H —CH₃

Cpd. R^(3′) R³ R^(3″) R⁴ = R⁵ F-1 —CH₃ H —CH₃ H F-2 —CH₂CH₃ H —CH₂CH₃ HF-3 iso-propyl H iso-propyl H F-4 iso-butyl H iso-butyl H F-5

H

H F-6

H

H F-7 —CH₂CH₃ H —CH₃ H F-8 —CH₃ H —CH₂CH₃ H F-9 —CH₃ —CH₃ H H F-10—CH₂CH₃ —CH₂CH₃ H H F-11 iso-butyl iso-butyl H H F-12 —CH₂CH₃ —CH₃ H HF-13 —CH₃ —CH₂CH₃ H H F-14 —CH₃ H —CH₃ —CH₂CH₃ F-15 —CH₂CH₃ H —CH₂CH₃—CH₂CH₃ F-16 iso-propyl H iso-propyl —CH₂CH₃ F-17 iso-butyl H iso-butyl—CH₂CH₃ F-18

H

—CH₂CH₃ F-19

H

—CH₂CH₃ F-20 —CH₂CH₃ H —CH₃ —CH₂CH₃ F-21 —CH₃ H —CH₂CH₃ —CH₂CH₃ F-22—CH₃ —CH₃ H —CH₂CH₃ F-23 —CH₂CH₃ —CH₂CH₃ H —CH₂CH₃ F-24 iso-butyliso-butyl H —CH₂CH₃ F-25 —CH₂CH₃ —CH₃ H —CH₂CH₃ F-26 —CH₃ —CH₂CH₃ H—CH₂CH₃ F-27 —CH₃ H —CH₃ iso-propyl F-28 —CH₂CH₃ H —CH₂CH₃ iso-propylF-29 iso-propyl H iso-propyl iso-propyl F-30 iso-butyl H iso-butyliso-propyl F-31

H

iso-propyl F-32

H

iso-propyl F-33 —CH₂CH₃ H —CH₃ iso-propyl F-34 —CH₃ H —CH₂CH₃ iso-propylF-35 —CH₃ —CH₃ H iso-propyl F-36 —CH₂CH₃ —CH₂CH₃ H iso-propyl F-37iso-butyl iso-butyl H iso-propyl F-38 —CH₂CH₃ —CH₃ H iso-propyl F-39—CH₃ —CH₂CH₃ H iso-propyl F-40 —CH₃ H —CH₃ iso-butyl F-41 —CH₂CH₃ H—CH₂CH₃ iso-butyl F-42 iso-propyl H iso-propyl iso-butyl F-43 iso-butylH iso-butyl iso-butyl F-44

H

iso-butyl F-45

H

iso-butyl F-46 —CH₂CH₃ H —CH₃ iso-butyl F-47 —CH₃ H —CH₂CH₃ iso-butylF-48 —CH₃ —CH₃ H iso-butyl F-49 —CH₂CH₃ —CH₂CH₃ H iso-butyl F-50iso-butyl iso-butyl H iso-butyl F-51 —CH₂CH₃ —CH₃ H iso-butyl F-52 —CH₃—CH₂CH₃ H iso-butyl F-53 —CH₃ —CH₃ H tert-butyl F-54 —CH₂CH₃ —CH₂CH₃ Htert-butyl F-55 iso-propyl iso-propyl H tert-butyl F-56 iso-butyliso-butyl H tert-butyl F-57 neopentyl neopentyl H tert-butyl F-58 —CH₃—CH₂CH₃ H tert-butyl F-59

H tert-butyl F-60

H tert-butyl F-61 —CH₃ —CH₃ —CH₃ tert-butyl F-62 ethyl ethyl —CH₃tert-butyl F-63 iso-propyl iso-propyl —CH₃ tert-butyl F-64 —CH₃ —CH₃iso-propyl tert-butyl F-65 ethyl ethyl iso-propyl tert-butyl E-66iso-propyl iso-propyl iso-propyl tert-butyl F-67 —CH₃ —CH₃ H tert-butylF-68 H H —CH₃ H F-69 H H —CH₂CH₃ H F-70 H H iso-propyl H F-71 H Hiso-butyl H F-72 H H

H F-73 H H

H F-74 H —CH₃ H H F-75 H —CH₃ H H F-76 H —CH₂CH₃ H H F-77 H iso-propyl HH F-78 H iso-butyl H H F-79 H

H H F-80 H

H H F-81 —CH₃ H —CH₃ —CH₃ F-82 —CH₂CH₃ H —CH₂CH₃ —CH₃ F-83 iso-propyl Hiso-propyl —CH₃ F-84 iso-butyl H iso-butyl —CH₃ F-85

H

—CH₃ F-86

H

—CH₃ F-87 —CH₂CH₃ H —CH₃ —CH₃ F-88 —CH₃ H —CH₂CH₃ —CH₃ F-89 —CH₃ —CH₃ H—CH₃ F-90 —CH₂CH₃ —CH₂CH₃ H —CH₃ F-91 iso-butyl iso-butyl H —CH₃ F-92—CH₂CH₃ —CH₃ H —CH₃ F-93 —CH₃ —CH₂CH₃ H —CH₃

Cpd. R^(3′) R³ R^(3″) R⁴ = R⁵ F′-1 —CH₃ H —CH₃ H F′-2 —CH₂CH₃ H —CH₂CH₃H F′-3 iso-propyl H iso-propyl H F′-4 iso-butyl H iso-butyl H F′-5

H

H F′-6

H

H F′-7 —CH₂CH₃ H —CH₃ H F′-8 —CH₃ H —CH₂CH₃ H F′-9 —CH₃ —CH₃ H H F′-10—CH₂CH₃ —CH₂CH₃ H H F′-11 iso-butyl iso-butyl H H F′-12 —CH₂CH₃ —CH₃ H HF′-13 —CH₃ —CH₂CH₃ H H F′-14 —CH₃ H —CH₃ —CH₂CH₃ F′-15 —CH₂CH₃ H —CH₂CH₃—CH₂CH₃ F′-16 iso-propyl H iso-propyl —CH₂CH₃ F′-17 iso-butyl Hiso-butyl —CH₂CH₃ F′-18

H

—CH₂CH₃ F′-19

H

—CH₂CH₃ F′-20 —CH₂CH₃ H —CH₃ —CH₂CH₃ F′-21 —CH₃ H —CH₂CH₃ —CH₂CH₃ F′-22—CH₃ —CH₃ H —CH₂CH₃ F′-23 —CH₂CH₃ —CH₂CH₃ H —CH₂CH₃ F′-24 iso-butyliso-butyl H —CH₂CH₃ F′-25 —CH₂CH₃ —CH₃ H —CH₂CH₃ F′-26 —CH₃ —CH₂CH₃ H—CH₂CH₃ F′-27 —CH₃ H —CH₃ iso-propyl F′-28 —CH₂CH₃ H —CH₂CH₃ iso-propylF′-29 iso-propyl H iso-propyl iso-propyl F′-30 iso-butyl H iso-butyliso-propyl F′-31

H

iso-propyl F′-32

H

iso-propyl F′-33 —CH₂CH₃ H —CH₃ iso-propyl F′-34 —CH₃ H —CH₂CH₃iso-propyl F′-35 —CH₃ —CH₃ H iso-propyl F′-36 —CH₂CH₃ —CH₂CH₃ Hiso-propyl F′-37 iso-butyl iso-butyl H iso-propyl F′-38 —CH₂CH₃ —CH₃ Hiso-propyl F′-39 —CH₃ —CH₂CH₃ H iso-propyl F′-40 —CH₃ H —CH₃ iso-butylF′-41 —CH₂CH₃ H —CH₂CH₃ iso-butyl F′-42 iso-propyl H iso-propyliso-butyl F′-43 iso-butyl H iso-butyl iso-butyl F′-44

H

iso-butyl F′-45

H

iso-butyl F′-46 —CH₂CH₃ H —CH₃ iso-butyl F′-47 —CH₃ H —CH₂CH₃ iso-butylF′-48 —CH₃ —CH₃ H iso-butyl F′-49 —CH₂CH₃ —CH₂CH₃ H iso-butyl F′-50iso-butyl iso-butyl H iso-butyl F′-51 —CH₂CH₃ —CH₃ H iso-butyl F′-52—CH₃ —CH₂CH₃ H iso-butyl F′-53 H H —CH₃ H F′-54 H H —CH₂CH₃ H F′-55 H Hiso-propyl H F′-56 H H iso-butyl H F′-57 H H

H F′-58 H H

H F′-59 H —CH₃ H H F′-60 H —CH₃ H H F′-61 H —CH₂CH₃ H H F′-62 Hiso-propyl H H F′-63 H iso-butyl H H F′-64 H

H H F′-65 H

H H F′-66 —CH₃ H —CH₃ —CH₃ F′-67 —CH₂CH₃ H —CH₂CH₃ —CH₃ F′-68 iso-propylH iso-propyl —CH₃ F′-69 iso-butyl H iso-butyl —CH₃ F′-70

H

—CH₃ F′-71

H

—CH₃ F′-72 —CH₂CH₃ H —CH₃ —CH₃ F′-73 —CH₃ H —CH₂CH₃ —CH₃ F′-74 —CH₃ —CH₃H —CH₃ F′-75 —CH₂CH₃ —CH₂CH₃ H —CH₃ F′-76 iso-butyl iso-butyl H —CH₃F′-77 —CH₂CH₃ —CH₃ H —CH₃ F′-78 —CH₃ —CH₂CH₃ H —CH₃

Cpd. R^(3′) R³ R⁴ = R⁵ G-1 H H H G-2 —CH₃ H H G-3 —CH₂CH₃ H H G-4iso-propyl H H G-5 iso-butyl H H G-6

H H G-7

H H G-8 H H H G-9 H —CH₃ H G-10 H —CH₂CH₃ H G-11 H iso-propyl H G-12 Hiso-butyl H G-13 H

H G-14 H

H G-15 —CH₃ —CH₃ H G-16 —CH₂CH₃ —CH₂CH₃ H G-17 iso-propyl iso-propyl HG-18 iso-butyl iso-butyl H G-19 —CH₃ —CH₂CH₃ H G-20 —CH₂CH₃ —CH₃ H G-21H H —CH₂CH₃ G-22 —CH₃ H —CH₂CH₃ G-23 —CH₂CH₃ H —CH₂CH₃ G-24 iso-propyl H—CH₂CH₃ G-25 iso-butyl H —CH₂CH₃ G-26

H —CH₂CH₃ G-27

H —CH₂CH₃ G-28 H H —CH₂CH₃ G-29 H —CH₃ —CH₂CH₃ G-30 H —CH₂CH₃ —CH₂CH₃G-31 H iso-propyl —CH₂CH₃ G-32 H iso-butyl —CH₂CH₃ G-33 H

—CH₂CH₃ G-34 H

—CH₂CH₃ G-35 —CH₃ —CH₃ —CH₂CH₃ G-36 —CH₂CH₃ —CH₂CH₃ —CH₂CH₃ G-37iso-propyl iso-propyl —CH₂CH₃ G-38 iso-butyl iso-butyl —CH₂CH₃ G-39 —CH₃—CH₂CH₃ —CH₂CH₃ G-40 —CH₂CH₃ —CH₃ —CH₂CH₃ G-41 H H iso-propyl G-42 —CH₃H iso-propyl G-43 —CH₂CH₃ H iso-propyl G-44 iso-propyl H iso-propyl G-45iso-butyl H iso-propyl G-46

H iso-propyl G-47

H iso-propyl G-48 H H iso-propyl G-49 H —CH₃ iso-propyl G-50 H —CH₂CH₃iso-propyl G-51 H iso-propyl iso-propyl G-52 H iso-butyl iso-propyl G-53H

iso-propyl G-54 H

iso-propyl G-55 —CH₃ —CH₃ iso-propyl G-56 —CH₂CH₃ —CH₂CH₃ iso-propylG-57 iso-propyl iso-propyl iso-propyl G-58 iso-butyl iso-butyliso-propyl G-59 —CH₃ —CH₂CH₃ iso-propyl G-60 —CH₂CH₃ —CH₃ iso-propylG-61 H H iso-butyl G-62 —CH₃ H iso-butyl G-63 —CH₂CH₃ H iso-butyl G-64iso-propyl H iso-butyl G-65 iso-butyl H iso-butyl G-66

H iso-butyl G-67

H iso-butyl G-68 H H iso-butyl G-69 H —CH₃ iso-butyl G-70 H —CH₂CH₃iso-butyl G-71 H iso-propyl iso-butyl G-72 H iso-butyl iso-butyl G-73 H

iso-butyl G-74 H

iso-butyl G-75 —CH₃ —CH₃ iso-butyl G-76 —CH₂CH₃ —CH₂CH₃ iso-butyl G-77iso-propyl iso-propyl iso-butyl G-78 iso-butyl iso-butyl iso-butyl G-79—CH₃ —CH₂CH₃ iso-butyl G-80 —CH₂CH₃ —CH₃ iso-butyl G-81 H H CH₃ G-82—CH₃ H CH₃ G-83 —CH₂CH₃ H CH₃ G-84 iso-propyl H CH₃ G-85 iso-butyl H CH₃G-86

H CH₃ G-87

H CH₃ G-88 H H CH₃ G-89 H —CH₃ CH₃ G-90 H —CH₂CH₃ CH₃ G-91 H iso-propylCH₃ G-92 H iso-butyl CH₃ G-93 H

CH₃ G-94 H

CH₃ G-95 —CH₃ —CH₃ CH₃ G-96 —CH₂CH₃ —CH₂CH₃ CH₃ G-97 iso-propyliso-propyl CH₃ G-98 iso-butyl iso-butyl CH₃ G-99 —CH₃ —CH₂CH₃ CH₃ G-100—CH₂CH₃ —CH₃ CH₃

Cpd. R^(3′) R³ R⁴ = R⁵ H-1 H H H H-2 —CH₃ H H H-3 —CH₂CH₃ H H H-4iso-propyl H H H-5 iso-butyl H H H-6

H H H-7

H H H-8 H H H H-9 H —CH₃ H H-10 H —CH₂CH₃ H H-11 H iso-propyl H H-12 Hiso-butyl H H-13 H

H H-14 H

H H-15 —CH₃ —CH₃ H H-16 —CH₂CH₃ —CH₂CH₃ H H-17 iso-propyl iso-propyl HH-18 iso-butyl iso-butyl H H-19 —CH₃ —CH₂CH₃ H H-20 —CH₂CH₃ —CH₃ H H-21H H —CH₂CH₃ H-22 —CH₃ H —CH₂CH₃ H-23 —CH₂CH₃ H —CH₂CH₃ H-24 iso-propyl H—CH₂CH₃ H-25 iso-butyl H —CH₂CH₃ H-26

H —CH₂CH₃ H-27

H —CH₂CH₃ H-28 H H —CH₂CH₃ H-29 H —CH₃ —CH₂CH₃ H-30 H —CH₂CH₃ —CH₂CH₃H-31 H iso-propyl —CH₂CH₃ H-32 H iso-butyl —CH₂CH₃ H-33 H

—CH₂CH₃ H-34 H

—CH₂CH₃ H-35 —CH₃ —CH₃ —CH₂CH₃ H-36 —CH₂CH₃ —CH₂CH₃ —CH₂CH₃ H-37iso-propyl iso-propyl —CH₂CH₃ H-38 iso-butyl iso-butyl —CH₂CH₃ H-39 —CH₃—CH₂CH₃ —CH₂CH₃ H-40 —CH₂CH₃ —CH₃ —CH₂CH₃ H-41 H H iso-propyl H-42 —CH₃H iso-propyl H-43 —CH₂CH₃ H iso-propyl H-44 iso-propyl H iso-propyl H-45iso-butyl H iso-propyl H-46

H iso-propyl H-47

H iso-propyl H-48 H H iso-propyl H-49 H —CH₃ iso-propyl H-50 H —CH₂CH₃iso-propyl H-51 H iso-propyl iso-propyl H-52 H iso-butyl iso-propyl H-53H

iso-propyl H-54 H

iso-propyl H-55 —CH₃ —CH₃ iso-propyl H-56 —CH₂CH₃ —CH₂CH₃ iso-propylH-57 iso-propyl iso-propyl iso-propyl H-58 iso-butyl iso-butyliso-propyl H-59 —CH₃ —CH₂CH₃ iso-propyl H-60 —CH₂CH₃ —CH₃ iso-propylH-61 H H iso-butyl H-62 —CH₃ H iso-butyl H-63 —CH₂CH₃ H iso-butyl H-64iso-propyl H iso-butyl H-65 iso-butyl H iso-butyl H-66

H iso-butyl H-67

H iso-butyl H-68 H H iso-butyl H-69 H —CH₃ iso-butyl H-70 H —CH₂CH₃iso-butyl H-71 H iso-propyl iso-butyl H-72 H iso-butyl iso-butyl H-73 H

iso-butyl H-74 H

iso-butyl H-75 —CH₃ —CH₃ iso-butyl H-76 —CH₂CH₃ —CH₂CH₃ iso-butyl H-77iso-propyl iso-propyl iso-butyl H-78 iso-butyl iso-butyl iso-butyl H-79—CH₃ —CH₂CH₃ iso-butyl H-80 —CH₂CH₃ —CH₃ iso-butyl H-81 H H CH₃ H-82—CH₃ H CH₃ H-83 —CH₂CH₃ H CH₃ H-84 iso-propyl H CH₃ H-85 iso-butyl H CH₃H-86

H CH₃ H-87

H CH₃ H-88 H H CH₃ H-89 H —CH₃ CH₃ H-90 H —CH₂CH₃ CH₃ H-91 H iso-propylCH₃ H-92 H iso-butyl CH₃ H-93 H

CH₃ H-94 H

CH₃ H-95 —CH₃ —CH₃ CH₃ H-96 —CH₂CH₃ —CH₂CH₃ CH₃ H-97 iso-propyliso-propyl CH₃ H-98 iso-butyl iso-butyl CH₃ H-99 —CH₃ —CH₂CH₃ CH₃ H-100—CH₂CH₃ —CH₃ CH₃

-   Among the above metal carbene-complexes A-1 to A-84, A′-1 to A′-70,    B-1 to B-84, B′-1 to B′-70, C-1 to C-163, C′-1 to C′-143, D-1 to    D-163, D′-1 to D′-143, E-1 to E-93, E′-1 to E′-78, F-1 to F-93, F′-1    to F′-78, G-1 to G-100, H-1 to H-100 the metal carbene-complexes A-1    to A-70, A′-1 to A′-70, B-1 to B-70, B′-1 to B′-70, C-1 to C-110,    C-125 to C-154, C-161 to C-163, C′-1 to C′-116, C′-141 to C′-143,    D-1 to D-110, D-125 to D-154, D-161 to D-163, D′-1 to D′-116, D′-141    to D′-143 are preferred. Among these metal carbene-complexes metal    carbene-complexes are more preferred, wherein R⁴ and R⁵ are H.

Metal carbene-complexes A-1 to A-70, A′-1 to A′-70, C-1 to C-110, C-125to C-154, C-161 to C-163, C′-1 to C′-116, C′-141 to C′-143 are morepreferred. Metal carbene-complexes A-1 to A-70, C-1 to C-110, C-125 toC-154, C-161 to C-163 are even more preferred.

Among these metal carbene-complexes metal carbene-complexes are morepreferred, wherein R⁴ and R⁵ are H.

Metal carbene-complexes A-2, A-3, A-4, A-6, A-14, C-126, C-127 and C-128are most preferred.

In another preferred embodiment the present invention is directed tometal complexes of formula (IIa), (IIb), or (IIc), wherein L is a ligand54 (D′),

wherein Z¹ and Z²are N, or Z¹ and Z²are CH; R* has the meaning of R′,R⁵⁴ has the meaning of R⁴, R^(54′) has the meaning of R^(4′), R⁵⁵ hasthe meaning of R⁵, R⁵⁶ has the meaning of R⁶ and R⁵⁷ has the meaning ofR⁷ and each group R is the same within one metal-carbene complex and is,for example, a group of formula

In said embodiment, the metal-carbene complex is preferably ametal-carbene complex of formula (IIa), (IIb), or (IIc), more preferablya metal-carbene complex of formula (IIIa), (IIIb), or (IIIc), mostpreferred a metal-carbene complex of formula (IIIa′), (IIIb′), or(IIIc′).

-   For R*, R⁵⁴, R^(54′), R⁵⁵, R⁵⁶ and R⁵⁷ the same preferences apply as    for R′, R⁴, R^(4′), R⁵, R⁶ and R⁷, respectively.

Preferably, Z¹ is CH, Z² is CH, R* and R′ are H, R⁵⁴ is the same as R⁴,R^(54′) is the same as

R^(4′), R⁵⁵ is the same as R⁵, R⁵⁶ is the same as R⁶ and R⁵⁷ is the sameas R⁷.

In said embodiment the metal-carbene complex is preferably ametal-carbene complex of formula

wherein R¹ and R² are independently of each other a C₁-C₅alkyl group,especially methyl, ethyl, iso-propyl, isobutyl and neopentyl; acyclopentyl or cyclohexyl group,R³ is H, or a C₁-C₄alkyl group; or

wherein R² is CF₃, especially a C₁-C₅alkyl group, especially methyl,ethyl, iso-propyl and isobutyl; a cyclopentyl or cyclohexyl group;R³ is H, a C₁-C₅alkyl group, especially methyl, ethyl, iso-propyl andisobutyl; a cyclopentyl or cyclohexyl group; andR^(3′) is H, a C₁-C₅alkyl group, especially methyl, ethyl, iso-propyland isobutyl; a cyclopentyl or cyclohexyl group; with the proviso thatin case one of R³ and R^(3′) is a cyclopentyl or cyclohexyl group, theother is H. R⁶ and R⁷ are independently of each other hydrogen, aC₁-C₈alkyl group, a C₃-C₆cycloalkyl group; orR⁶ and R⁷ form together a ring

with the proviso that if one of R⁶ and R⁷ is a C₁-C₈alkyl group, or aC₃-C₆cycloalkyl group, the other is H. R⁶ and R⁷ are preferably H. R⁴and R⁵ are preferably H.

Examples of metal carbene complexes are shown below:

Cpd. R¹ R² R³ R⁴ = R⁵ I-1 —CH₃ —CH₃ H H I-2 —CH₂CH₃ —CH₂CH₃ H H I-3iso-propyl iso-propyl H H I-4 iso-butyl iso-butyl H H I-5 neopentylneopentyl H H I-6 —CH₃ —CH₂CH₃ H H I-7

H H I-8

H H I-9 —CH₃ —CH₃ —CH₃ H I-10 ethyl ethyl —CH₃ H I-11 iso-propyliso-propyl —CH₃ H I-12 —CH₃ —CH₃ iso-propyl H I-13 ethyl ethyliso-propyl H I-14 iso-propyl iso-propyl iso-propyl H I-15 —CH₃ —CH₃ H—CH₃ I-16 —CH₂CH₃ —CH₂CH₃ H —CH₃ I-17 iso-propyl iso-propyl H —CH₃ I-18iso-butyl iso-butyl H —CH₃ I-19 neopentyl neopentyl H —CH₃ I-20 —CH₃—CH₂CH₃ H —CH₃ I-21

H —CH₃ I-22

H —CH₃ I-23 —CH₃ —CH₃ —CH₃ —CH₃ I-24 ethyl ethyl —CH₃ —CH₃ I-25iso-propyl iso-propyl —CH₃ —CH₃ I-26 —CH₃ —CH₃ iso-propyl —CH₃ I-27ethyl ethyl iso-propyl —CH₃ I-28 iso-propyl iso-propyl iso-propyl —CH₃I-29 —CH₃ —CH₃ H —CH₂CH₃ I-30 —CH₂CH₃ —CH₂CH₃ H —CH₂CH₃ I-31 iso-propyliso-propyl H —CH₂CH₃ I-32 iso-butyl iso-butyl H —CH₂CH₃ I-33 —CH₃—CH₂CH₃ H —CH₂CH₃ I-34 neopentyl neopentyl H —CH₂CH₃ I-35

H —CH₂CH₃ I-36

H —CH₂CH₃ I-37 —CH₃ —CH₃ —CH₃ —CH₂CH₃ I-38 ethyl ethyl —CH₃ —CH₂CH₃ I-39iso-propyl iso-propyl —CH₃ —CH₂CH₃ I-40 —CH₃ —CH₃ iso-propyl —CH₂CH₃I-41 ethyl ethyl iso-propyl —CH₂CH₃ I-42 iso-propyl iso-propyliso-propyl —CH₂CH₃ I-43 —CH₃ —CH₃ H iso-propyl I-44 —CH₂CH₃ —CH₂CH₃ Hiso-propyl I-45 iso-propyl iso-propyl H iso-propyl I-46 iso-butyliso-butyl H iso-propyl I-47 neopentyl neopentyl H iso-propyl I-48 —CH₃—CH₂CH₃ H iso-propyl I-49

H iso-propyl I-50

H iso-propyl I-51 —CH₃ —CH₃ —CH₃ iso-propyl I-52 ethyl ethyl —CH₃iso-propyl I-53 iso-propyl iso-propyl —CH₃ iso-propyl I-54 —CH₃ —CH₃iso-propyl iso-propyl I-55 ethyl ethyl iso-propyl iso-propyl I-56iso-propyl iso-propyl iso-propyl iso-propyl I-57 —CH₃ —CH₃ H iso-butylI-58 —CH₂CH₃ —CH₂CH₃ H iso-butyl I-59 iso-propyl iso-propyl H iso-butylI-60 iso-butyl iso-butyl H iso-butyl I-61 neopentyl neopentyl Hiso-butyl I-62 —CH₃ —CH₂CH₃ H iso-butyl I-63

H iso-butyl I-64

H iso-butyl I-65 —CH₃ —CH₃ —CH₃ iso-butyl I-66 ethyl ethyl —CH₃iso-butyl I-67 iso-propyl iso-propyl —CH₃ iso-butyl I-68 —CH₃ —CH₃iso-propyl iso-butyl I-69 ethyl ethyl iso-propyl iso-butyl I-70iso-propyl iso-propyl iso-propyl iso-butyl

Cpd. R² R^(3′) R³ R⁴ = R⁵ J-1 —CH₃ —CH₃ H H J-2 —CH₂CH₃ —CH₂CH₃ H H J-3iso-propyl iso-propyl H H J-4 iso-butyl iso-butyl H H J-5

H H J-6

H H J-7 —CH₂CH₃ —CH₃ H H J-8 —CH₃ —CH₂CH₃ H H J-9 —CH₃ H —CH₃ H J-10—CH₂CH₃ H —CH₂CH₃ H J-11 iso-propyl H iso-propyl H J-12 iso-butyl Hiso-butyl H J-13

H

H J-14

H

H J-15 —CH₂CH₃ H —CH₃ H J-16 —CH₃ H —CH₂CH₃ H J-17 —CH₃ —CH₃ —CH₃ H J-18—CH₂CH₃ —CH₃ —CH₃ H J-19 iso-propyl —CH₃ —CH₃ H J-20 iso-butyl —CH₃ —CH₃H J-21

—CH₃ —CH₃ H J-22

—CH₃ —CH₃ H J-23 —CH₃ —CH₃ H —CH₃ J-24 —CH₂CH₃ —CH₂CH₃ H —CH₃ J-25iso-propyl iso-propyl H —CH₃ J-26 iso-butyl iso-butyl H —CH₃ J-27

H —CH₃ J-28

H —CH₃ J-29 —CH₂CH₃ —CH₃ H —CH₃ J-30 —CH₃ —CH₂CH₃ H —CH₃ J-31 —CH₃ H—CH₃ —CH₃ J-32 —CH₂CH₃ H —CH₂CH₃ —CH₃ J-33 iso-propyl H iso-propyl —CH₃J-34 iso-butyl H iso-butyl —CH₃ J-35

H

—CH₃ J-36

H

—CH₃ J-37 —CH₂CH₃ H —CH₃ —CH₃ J-38 —CH₃ H —CH₂CH₃ —CH₃ J-39 —CH₃ —CH₃—CH₃ —CH₃ J-40 —CH₂CH₃ —CH₃ —CH₃ —CH₃ J-41 iso-propyl —CH₃ —CH₃ —CH₃J-42 iso-butyl —CH₃ —CH₃ —CH₃ J-43

—CH₃ —CH₃ —CH₃ J-44

—CH₃ —CH₃ —CH₃ J-45 —CH₃ —CH₃ H —CH₂CH₃ J-46 —CH₂CH₃ —CH₂CH₃ H —CH₂CH₃J-47 iso-propyl iso-propyl H —CH₂CH₃ J-48 iso-butyl iso-butyl H —CH₂CH₃J-49

H —CH₂CH₃ J-50

H —CH₂CH₃ J-51 —CH₂CH₃ —CH₃ H —CH₂CH₃ J-52 —CH₃ —CH₂CH₃ H —CH₂CH₃ J-53—CH₃ H —CH₃ —CH₂CH₃ J-54 —CH₂CH₃ H —CH₂CH₃ —CH₂CH₃ J-55 iso-propyl Hiso-propyl —CH₂CH₃ J-56 iso-butyl H iso-butyl —CH₂CH₃ J-57

H

—CH₂CH₃ J-58

H

—CH₂CH₃ J-59 —CH₂CH₃ H —CH₃ —CH₂CH₃ J-60 —CH₃ H —CH₂CH₃ —CH₂CH₃ J-61—CH₃ —CH₃ —CH₃ —CH₂CH₃ J-62 —CH₂CH₃ —CH₃ —CH₃ —CH₂CH₃ J-63 iso-propyl—CH₃ —CH₃ —CH₂CH₃ J-64 iso-butyl —CH₃ —CH₃ —CH₂CH₃ J-65

—CH₃ —CH₃ —CH₂CH₃ J-66

—CH₃ —CH₃ —CH₂CH₃ J-67 —CH₃ —CH₃ H iso- propyl J-68 —CH₂CH₃ —CH₂CH₃ Hiso- propyl J-69 iso-propyl iso-propyl H iso- propyl J-70 iso-butyliso-butyl H iso- propyl J-71

H iso- propyl J-72

H iso- propyl J-73 —CH₂CH₃ —CH₃ H iso- propyl J-74 —CH₃ —CH₂CH₃ H iso-propyl J-75 —CH₃ H —CH₃ iso- propyl J-76 —CH₂CH₃ H —CH₂CH₃ iso- propylJ-77 iso-propyl H iso-propyl iso- propyl J-78 iso-butyl H iso-butyl iso-propyl J-79

H

iso- propyl J-80

H

iso- propyl J-81 —CH₂CH₃ H —CH₃ iso- propyl J-82 —CH₃ H —CH₂CH₃ iso-propyl J-83 —CH₃ —CH₃ —CH₃ iso- propyl J-84 —CH₂CH₃ —CH₃ —CH₃ iso-propyl J-85 iso-propyl —CH₃ —CH₃ iso- propyl J-86 iso-butyl —CH₃ —CH₃iso- propyl J-87

—CH₃ —CH₃ iso- propyl J-88

—CH₃ —CH₃ iso- propyl J-89 —CH₃ —CH₃ H iso-butyl J-90 —CH₂CH₃ —CH₂CH₃ Hiso-butyl J-91 iso-propyl iso-propyl H iso-butyl J-92 iso-butyliso-butyl H iso-butyl J-93

H iso-butyl J-94

H iso-butyl J-95 —CH₂CH₃ —CH₃ H iso-butyl J-96 —CH₃ —CH₂CH₃ H iso-butylJ-97 —CH₃ H —CH₃ iso-butyl J-98 —CH₂CH₃ H —CH₂CH₃ iso-butyl J-99iso-propyl H iso-propyl iso-butyl J-100 iso-butyl H iso-butyl iso-butylJ-101

H

iso-butyl J-102

H

iso-butyl J-103 —CH₂CH₃ H —CH₃ iso-butyl J-104 —CH₃ H —CH₂CH₃ iso-butylJ-105 —CH₃ —CH₃ —CH₃ iso-butyl J-106 —CH₂CH₃ —CH₃ —CH₃ iso-butyl J-107iso-propyl —CH₃ —CH₃ iso-butyl J-108 iso-butyl —CH₃ —CH₃ iso-butyl J-109

—CH₃ —CH₃ iso-butyl J-110

—CH₃ —CH₃ iso-butyl J-111 —CH₃ H H H J-112 —CH₂CH₃ H H H J-113iso-propyl H H H J-114 iso-butyl H H H J-115

H H H J-116

H H H J-117 —CH₃ H H —CH₃ J-118 —CH₂CH₃ H H —CH₃ J-119 iso-propyl H H—CH₃ J-120 iso-butyl H H —CH₃ J-121

H H —CH₃ J-122

H H —CH₃ J-123 —CH₃ H H —CH₂CH₃ J-124 —CH₂CH₃ H H —CH₂CH₃ J-125iso-propyl H H —CH₂CH₃ J-126 iso-butyl H H —CH₂CH₃ J-127

H H —CH₂CH₃ J-128

H H —CH₂CH₃ J-129 —CH₃ H H iso- propyl J-130 —CH₂CH₃ H H iso- propylJ-131 iso-propyl H H iso- propyl J-132 iso-butyl H H iso- propyl J-133

H H iso- propyl J-134

H H iso- propyl J-135 —CH₃ H H iso-butyl J-136 —CH₂CH₃ H H iso-butylJ-137 iso-propyl H H iso-butyl J-138 iso-butyl H H iso-butyl J-139

H H iso-butyl J-140

H H iso-butyl

Cpd. R^(3′) R³ R^(3″) R⁴ = R⁵ K-1 —CH₃ H —CH₃ H K-2 —CH₂CH₃ H —CH₂CH₃ HK-3 iso-propyl H iso-propyl H K-4 iso-butyl H iso-butyl H K-5

H

H K-6

H

H K-7 —CH₂CH₃ H —CH₃ H K-8 —CH₃ H —CH₂CH₃ H K-9 —CH₃ —CH₃ H H K-10—CH₂CH₃ —CH₂CH₃ H H K-11 iso-butyl iso-butyl H H K-12 —CH₂CH₃ —CH₃ H HK-13 —CH₃ —CH₂CH₃ H H K-14 —CH₃ H —CH₃ —CH₂CH₃ K-15 —CH₂CH₃ H —CH₂CH₃—CH₂CH₃ K-16 iso-propyl H iso-propyl —CH₂CH₃ K-17 iso-butyl H iso-butyl—CH₂CH₃ K-18

H

—CH₂CH₃ K-19

H

—CH₂CH₃ K-20 —CH₂CH₃ H —CH₃ —CH₂CH₃ K-21 —CH₃ H —CH₂CH₃ —CH₂CH₃ K-22—CH₃ —CH₃ H —CH₂CH₃ K-23 —CH₂CH₃ —CH₂CH₃ H —CH₂CH₃ K-24 iso-butyliso-butyl H —CH₂CH₃ K-25 —CH₂CH₃ —CH₃ H —CH₂CH₃ K-26 —CH₃ —CH₂CH₃ H—CH₂CH₃ K-27 —CH₃ H —CH₃ iso- propyl K-28 —CH₂CH₃ H —CH₂CH₃ iso- propylK-29 iso-propyl H iso-propyl iso- propyl K-30 iso-butyl H iso-butyl iso-propyl K-31

H

iso propyl K-32

H

iso- propyl K-33 —CH₂CH₃ H —CH₃ iso- propyl K-34 —CH₃ H —CH₂CH₃ iso-propyl K-35 —CH₃ —CH₃ H iso- propyl K-36 —CH₂CH₃ —CH₂CH₃ H iso- propylK-37 iso-butyl iso-butyl H iso- propyl K-38 —CH₂CH₃ —CH₃ H iso- propylK-39 —CH₃ —CH₂CH₃ H iso- propyl K-40 —CH₃ H —CH₃ iso-butyl K-41 —CH₂CH₃H —CH₂CH₃ iso-butyl K-42 iso-propyl H iso-propyl iso-butyl K-43iso-butyl H iso-butyl iso-butyl K-44

H

iso-butyl K-45

H

iso-butyl K-46 —CH₂CH₃ H —CH₃ iso-butyl K-47 —CH₃ H —CH₂CH₃ iso-butylK-48 —CH₃ —CH₃ H iso-butyl K-49 —CH₂CH₃ —CH₂CH₃ H iso-butyl K-50iso-butyl iso-butyl H iso-butyl K-51 —CH₂CH₃ —CH₃ H iso-butyl K-52 —CH₃—CH₂CH₃ H iso-butyl K-53 H H —CH₃ H K-54 H H —CH₂CH₃ H K-55 H Hiso-propyl H K-56 H H iso-butyl H K-57 H H

H K-58 H H

H K-59 H —CH₃ H H K-60 H —CH₃ H H K-61 H —CH₂CH₃ H H K-62 H iso-propyl HH K-63 H iso-butyl H H K-64 H

H H K-65 H

H H K-66 —CH₃ H —CH₃ —CH₃ K-67 —CH₂CH₃ H —CH₂CH₃ —CH₃ K-68 iso-propyl Hiso-propyl —CH₃ K-69 iso-butyl H iso-butyl —CH₃ K-70

H

—CH₃ K-71

H

—CH₃ K-72 —CH₂CH₃ H —CH₃ —CH₃ K-73 —CH₃ H —CH₂CH₃ —CH₃ K-74 —CH₃ —CH₃ H—CH₃ K-75 —CH₂CH₃ —CH₂CH₃ H —CH₃ K-76 iso-butyl iso-butyl H —CH₃ K-77—CH₂CH₃ —CH₃ H —CH₃ K-78 —CH₃ —CH₂CH₃ H —CH₃

Cpd. R^(3′) R³ R⁴ = R⁵ L-1 H H H L-2 —CH₃ H H L-3 —CH₂CH₃ H H L-4iso-propyl H H L-5 iso-butyl H H L-6

H H L-7

H H L-8 H H H L-9 H —CH₃ H L-10 H —CH₂CH₃ H L-11 H iso-propyl H L-12 Hiso-butyl H L-13 H

H L-14 H

H L-15 —CH₃ —CH₃ H L-16 —CH₂CH₃ —CH₂CH₃ H L-17 iso-propyl iso-propyl HL-18 iso-butyl iso-butyl H L-19 —CH₃ —CH₂CH₃ H L-20 —CH₂CH₃ —CH₃ H L-21H H —CH₂CH₃ L-22 —CH₃ H —CH₂CH₃ L-23 —CH₂CH₃ H —CH₂CH₃ L-24 iso-propyl H—CH₂CH₃ L-25 iso-butyl H —CH₂CH₃ L-26

H —CH₂CH₃ L-27

H —CH₂CH₃ L-28 H H —CH₂CH₃ L-29 H —CH₃ —CH₂CH₃ L-30 H —CH₂CH₃ —CH₂CH₃L-31 H iso-propyl —CH₂CH₃ L-32 H iso-butyl —CH₂CH₃ L-33 H

—CH₂CH₃ L-34 H

—CH₂CH₃ L-35 —CH₃ —CH₃ —CH₂CH₃ L-36 —CH₂CH₃ —CH₂CH₃ —CH₂CH₃ L-37iso-propyl iso-propyl —CH₂CH₃ L-38 iso-butyl iso-butyl —CH₂CH₃ L-39 —CH₃—CH₂CH₃ —CH₂CH₃ L-40 —CH₂CH₃ —CH₃ —CH₂CH₃ L-41 H H iso-propyl L-42 —CH₃H iso-propyl L-43 —CH₂CH₃ H iso-propyl L-44 iso-propyl H iso-propyl L-45iso-butyl H iso-propyl L-46

H iso-propyl L-47

H iso-propyl L-48 H H iso-propyl L-49 H —CH₃ iso-propyl L-50 H —CH₂CH₃iso-propyl L-51 H iso-propyl iso-propyl L-52 H iso-butyl iso-propyl L-53H

iso-propyl L-54 H

iso-propyl L-55 —CH₃ —CH₃ iso-propyl L-56 —CH₂CH₃ —CH₂CH₃ iso-propylL-57 iso-propyl iso-propyl iso-propyl L-58 iso-butyl iso-butyliso-propyl L-59 —CH₃ —CH₂CH₃ iso-propyl L-60 —CH₂CH₃ —CH₃ iso-propylL-61 H H iso-butyl L-62 —CH₃ H iso-butyl L-63 —CH₂CH₃ H iso-butyl L-64iso-propyl H iso-butyl L-65 iso-butyl H iso-butyl L-66

H iso-butyl L-67

H iso-butyl L-68 H H iso-butyl L-69 H —CH₃ iso-butyl L-70 H —CH₂CH₃iso-butyl L-71 H iso-propyl iso-butyl L-72 H iso-butyl iso-butyl L-73 H

iso-butyl L-74 H

iso-butyl L-75 —CH₃ —CH₃ iso-butyl L-76 —CH₂CH₃ —CH₂CH₃ iso-butyl L-77iso-propyl iso-propyl iso-butyl L-78 iso-butyl iso-butyl iso-butyl L-79—CH₃ —CH₂CH₃ iso-butyl L-80 —CH₂CH₃ —CH₃ iso-butyl L-81 H H CH₃ L-82—CH₃ H CH₃ L-83 —CH₂CH₃ H CH₃ L-84 iso-propyl H CH₃ L-85 iso-butyl H CH₃L-86

H CH₃ L-87

H CH₃ L-88 H H CH₃ L-89 H —CH₃ CH₃ L-90 H —CH₂CH₃ CH₃ L-91 H iso-propylCH₃ L-92 H iso-butyl CH₃ L-93 H

CH₃ L-94 H

CH₃ L-95 —CH₃ —CH₃ CH₃ L-96 —CH₂CH₃ —CH₂CH₃ CH₃ L-97 iso-propyliso-propyl CH₃ L-98 iso-butyl iso-butyl CH₃ L-99 —CH₃ —CH₂CH₃ CH₃ L-100—CH₂CH₃ —CH₃ CH₃

Among the above metal carbene-complexes I-1 to I-70, J-1 to J-140, K-1to K-78 and L-1 to L-100 the metal carbene-complexes I-1 to I-114 andJ-1 to J-116 are preferred. Among these metal carbene-complexes metalcarbene-complexes are more preferred, wherein R⁴ and R⁵ are H.

Metal carbene-complexes I-1 to I-14 and J-1 to J-116 are more preferred.Among these metal carbene-complexes metal carbene-complexes are morepreferred, wherein R⁴ and R⁵ are H.

If R³ and R^(3′), or R¹ and R^(3′) together form a group of formula

the following preferences apply:R³ and R^(3′) together form a group of formula

(

indicates the R^(3′) bonding,

indicates the R³ bonding);R³ and R^(3′) together form a group of formula

(

indicates the R³ bonding,

indicates the R^(3′) bonding);R¹ and R^(3′) together form a group of formula

(

indicates the R¹ bonding,

indicates the R³ bonding);R¹ and R^(3′) together form a group of formula

(

indicates the R^(3′) bonding,

indicates the R¹ bonding);

In a preferred embodiment the present invention is directed to metalcomplexes of formula

o is 0, 1, or 2 and m is 1, 2, or 3, the sum of m+o is 3.

X is O, or S, preferably O.

R¹ is H, C₁-C₅alkyl, cyclopentyl, or cyclohexyl; preferably C₁-C₅alkyl,more preferably methyl, ethyl, isopropyl, or isobutyl.

R² is H, C₁-C₅alkyl, cyclopentyl, or cyclohexyl; preferably C₁-C₅alkyl,more preferably methyl, ethyl, isopropyl, or isobutyl. In a preferredembodiment one of the groups R¹ and R² is C₁-C₅alkyl and the other groupis H. In a more preferred embodiment R¹ and R² are C₁-C₅alkyl.

R³ is H, C₁-C₅alkyl, cyclopentyl, or cyclohexyl; preferably H, methyl,ethyl, isopropyl, or isobutyl, more preferably H.

R⁴ and R⁵ are H, C₁-C₅alkyl, especially methyl, ethyl, isopropyl, orisobutyl; cyclopentyl, or cyclohexyl; preferably H.

L is preferably a group (X-1), (X-2), (X-3), (X-4), (X-5), (X-6), (X-7),(X-8), (X-9), (X-10), (X-11), (X-12), (X-13), (X-14), (X-15), (X-16),(X-17), (X-18), (X-19), (X-20), (X-21), (X-22), (X-23), (X-24), (X-25),(X-26), or (X-27); more preferably a group (X-1), (X-2), (X-3), or(X-4).

In said embodiment metal complexes of formula

are more preferred, wherein X, R¹, R², R³, R⁴, R⁵ and L are as definedabove.

In said embodiment metal complexes of formula (IVa′), (IVb′), (IVc′),(IVd′), (IVe′), (IVf′), (IVg′) and (IVh′) are even more preferred,wherein the substituents have the following meanings:

X is O.

R¹ is C₁-C₅alkyl, cyclopentyl, or cyclohexyl; preferably C₁-C₅alkyl,more preferably methyl, ethyl, isopropyl, or isobutyl.

R² is C₁-C₅alkyl, cyclopentyl, or cyclohexyl; preferably C₁-C₅alkyl,more preferably methyl, ethyl, isopropyl, or isobutyl.

R³ is H, C₁-C₅alkyl, cyclopentyl, or cyclohexyl; preferably H, methyl,ethyl, isopropyl, or isobutyl, more preferably H.

R⁴ and R⁵ are H, C₁-C₅alkyl, especially methyl, ethyl, isopropyl, orisobutyl; cyclopentyl, or cyclohexyl; preferably H.

L is preferably a group (X-1), (X-2), (X-3), (X-4), (X-5), (X-6), (X-7),(X-8), (X-9), (X-10), (X-11), (X-12), (X-13), (X-14), (X-15), (X-16),(X-17), (X-18), (X-19), (X-20), (X-21), (X-22), (X-23), (X-24), (X-25),(X-26), or (X-27); more preferably a group (X-1), (X-2), (X-3), or(X-4).

In said embodiment metal complexes of formula (IVa′), (IVb′), (IVc′),(IVd′), (IVe′), (IVf′), (IVg′) and (IVh′) are most preferred, whereinthe substituents have the following meanings:

X is O.

R¹ is C₁-C₅alkyl, more preferably methyl, ethyl, isopropyl, or isobutyl.

R² is C₁-C₅alkyl, more preferably methyl, ethyl, isopropyl, or isobutyl.

R³ is H, C₁-C₅alkyl, such as methyl, ethyl, isopropyl, or isobutyl; morepreferably H.

R⁴ and R⁵ are H.

L is a group (X-1), (X-2), (X-3), (X-4), (X-5), (X-6), (X-7), (X-8),(X-9), (X-10), (X-11), (X-12), (X-13), (X-14), (X-15), (X-16), (X-17),(X-18), (X-19), (X-20), (X-21), (X-22), (X-23), (X-24), (X-25), (X-26),or (X-27); more preferably a group (X-1), (X-2), (X-3), or (X-4).

Examples of metal complexes of formula (IVe′), (IVf′), (IVg′) and (IVh′)are shown below.

Cpd. R¹ R² R⁴ = R⁵ M-1 —CH₃ —CH₃ H M-2 —CH₂CH₃ —CH₂CH₃ H M-3 iso-propyliso-propyl H M-4 iso-butyl iso-butyl H M-5 neopentyl neopentyl H M-6—CH₃ —CH₂CH₃ H M-7

H M-8

H M-9 —CH₃ —CH₃ —CH₃ M-10 —CH₂CH₃ —CH₂CH₃ —CH₃ M-11 iso-propyliso-propyl —CH₃ M-12 iso-butyl iso-butyl —CH₃ M-13 neopentyl neopentyl—CH₃ M-14 —CH₃ —CH₂CH₃ —CH₃ M-15

—CH₃ M-16

—CH₃ M-17 —CH₃ —CH₃ —CH₂CH₃ M-18 —CH₂CH₃ —CH₂CH₃ —CH₂CH₃ M-19 iso-propyliso-propyl —CH₂CH₃ M-20 iso-butyl iso-butyl —CH₂CH₃ M-21 —CH₃ —CH₂CH₃—CH₂CH₃ M-22 neopentyl neopentyl —CH₂CH₃ M-23

—CH₂CH₃ M-24

—CH₂CH₃ M-25 —CH₃ —CH₃ iso-propyl M-26 —CH₂CH₃ —CH₂CH₃ iso-propyl M-27iso-propyl iso-propyl iso-propyl M-28 iso-butyl iso-butyl iso-propylM-29 neopentyl neopentyl iso-propyl M-30 —CH₃ —CH₂CH₃ iso-propyl M-31

iso-propyl M-32

iso-propyl M-33 —CH₃ —CH₃ iso-butyl M-34 —CH₂CH₃ —CH₂CH₃ iso-butyl M-35iso-propyl iso-propyl iso-butyl M-36 iso-butyl iso-butyl iso-butyl M-37neopentyl neopentyl iso-butyl M-38 —CH₃ —CH₂CH₃ iso-butyl M-39

iso-butyl M-40

iso-butyl

Cpd. R¹ R² R⁴ = R⁵ N-1 —CH₃ —CH₃ H N-2 —CH₂CH₃ —CH₂CH₃ H N-3 iso-propyliso-propyl H N-4 iso-butyl iso-butyl H N-5 neopentyl neopentyl H N-6—CH₃ —CH₂CH₃ H N-7

H N-8

H N-9 —CH₃ —CH₃ —CH₃ N-10 —CH₂CH₃ —CH₂CH₃ —CH₃ N-11 iso-propyliso-propyl —CH₃ N-12 iso-butyl iso-butyl —CH₃ N-13 neopentyl neopentyl—CH₃ N-14 —CH₃ —CH₂CH₃ —CH₃ N-15

—CH₃ N-16

—CH₃ N-17 —CH₃ —CH₃ —CH₂CH₃ N-18 —CH₂CH₃ —CH₂CH₃ —CH₂CH₃ N-19 iso-propyliso-propyl —CH₂CH₃ N-20 iso-butyl iso-butyl —CH₂CH₃ N-21 —CH₃ —CH₂CH₃—CH₂CH₃ N-22 neopentyl neopentyl —CH₂CH₃ N-23

—CH₂CH₃ N-24

—CH₂CH₃ N-25 —CH₃ —CH₃ iso-propyl N-26 —CH₂CH₃ —CH₂CH₃ iso-propyl N-27iso-propyl iso-propyl iso-propyl N-28 iso-butyl iso-butyl iso-propylN-29 neopentyl neopentyl iso-propyl N-30 —CH₃ —CH₂CH₃ iso-propyl N-31

iso-propyl N-32

iso-propyl N-33 —CH₃ —CH₃ iso-butyl N-34 —CH₂CH₃ —CH₂CH₃ iso-butyl N-35iso-propyl iso-propyl iso-butyl N-36 iso-butyl iso-butyl iso-butyl N-37neopentyl neopentyl iso-butyl N-38 —CH₃ —CH₂CH₃ iso-butyl N-39

iso-butyl N-40

iso-butyl

Cpd. R¹ R³ R⁴ = R⁵ O-1 —CH₃ —CH₃ H O-2 —CH₂CH₃ —CH₂CH₃ H O-3 iso-propyliso-propyl H O-4 iso-butyl iso-butyl H O-5 neopentyl neopentyl H O-6—CH₃ —CH₂CH₃ H O-7

H O-8

H O-9 —CH₃ —CH₃ —CH₃ O-10 —CH₂CH₃ —CH₂CH₃ —CH₃ O-11 iso-propyliso-propyl —CH₃ O-12 iso-butyl iso-butyl —CH₃ O-13 neopentyl neopentyl—CH₃ O-14 —CH₃ —CH₂CH₃ —CH₃ O-15

—CH₃ O-16

—CH₃ O-17 —CH₃ —CH₃ —CH₂CH₃ O-18 —CH₂CH₃ —CH₂CH₃ —CH₂CH₃ O-19 iso-propyliso-propyl —CH₂CH₃ O-20 iso-butyl iso-butyl —CH₂CH₃ O-21 —CH₃ —CH₂CH₃—CH₂CH₃ O-22 neopentyl neopentyl —CH₂CH₃ O-23

—CH₂CH₃ O-24

—CH₂CH₃ O-25 —CH₃ —CH₃ iso-propyl O-26 —CH₂CH₃ —CH₂CH₃ iso-propyl O-27iso-propyl iso-propyl iso-propyl O-28 iso-butyl iso-butyl iso-propylO-29 neopentyl neopentyl iso-propyl O-30 —CH₃ —CH₂CH₃ iso-propyl O-31

iso-propyl O-32

iso-propyl O-33 —CH₃ —CH₃ iso-butyl O-34 —CH₂CH₃ —CH₂CH₃ iso-butyl O-35iso-propyl iso-propyl iso-butyl O-36 iso-butyl iso-butyl iso-butyl O-37neopentyl neopentyl iso-butyl O-38 —CH₃ —CH₂CH₃ iso-butyl O-39

iso-butyl O-40

iso-butyl

Cpd. R¹ R³ R⁴ = R⁵ P-1 —CH₃ —CH₃ H P-2 —CH₂CH₃ —CH₂CH₃ H P-3 iso-propyliso-propyl H P-4 iso-butyl iso-butyl H P-5 neopentyl neopentyl H P-6—CH₃ —CH₂CH₃ H P-7

H P-8

H P-9 —CH₃ —CH₃ —CH₃ P-10 —CH₂CH₃ —CH₂CH₃ —CH₃ P-11 iso-propyliso-propyl —CH₃ P-12 iso-butyl iso-butyl —CH₃ P-13 neopentyl neopentyl—CH₃ P-14 —CH₃ —CH₂CH₃ —CH₃ P-15

—CH₃ P-16

—CH₃ P-17 —CH₃ —CH₃ —CH₂CH₃ P-18 —CH₂CH₃ —CH₂CH₃ —CH₂CH₃ P-19 iso-propyliso-propyl —CH₂CH₃ P-20 iso-butyl iso-butyl —CH₂CH₃ P-21 —CH₃ —CH₂CH₃—CH₂CH₃ P-22 neopentyl neopentyl —CH₂CH₃ P-23

—CH₂CH₃ P-24

—CH₂CH₃ P-25 —CH₃ —CH₃ iso-propyl P-26 —CH₂CH₃ —CH₂CH₃ iso-propyl P-27iso-propyl iso-propyl iso-propyl P-28 iso-butyl iso-butyl iso-propylP-29 neopentyl neopentyl iso-propyl P-30 —CH₃ —CH₂CH₃ iso-propyl P-31

iso-propyl P-32

iso-propyl P-33 —CH₃ —CH₃ iso-butyl P-34 —CH₂CH₃ —CH₂CH₃ iso-butyl P-35iso-propyl iso-propyl iso-butyl P-36 iso-butyl iso-butyl iso-butyl P-37neopentyl neopentyl iso-butyl P-38 —CH₃ —CH₂CH₃ iso-butyl P-39

iso-butyl P-40

iso-butyl

Among the above metal carbene-complexes M-1 to M-40, N-1 to N-40, 0-1 to0-40 and P-1 to P-40 the metal carbene-complexes M-1 to M-8, N-1 to N-8,0-1 to 0-8 and P-1 to P-8 are preferred.

In principal, L can also be a ligand

which is different from the ligand

wherein Z¹ and Z² are N, or Z¹ and Z² are CH, R* has the meaning of R′,R⁵⁴ has the meaning of R⁴, R^(54′) has the meaning of R^(4′), R⁵⁵ hasthe meaning of R⁵, R⁵⁶ has the meaning of R⁶ and R⁵⁷ has the meaning ofR⁷ and each group R is the same within one metal-carbene complex.

In said embodiment the present invention is directed to complexes offormula D₂MD′ (Va), or D₂MD′ (Vb). Complexes of formula D₂MD′ (Va) arepreferred.

For R*, R⁵⁴, R^(54′), R⁵⁵, R⁵⁶ and R⁵⁷ the same preferences apply as forR¹, R⁴, R^(4′), R⁵, R⁶ and R⁷, respectively.

Preferably, Z¹ is CH, Z² is CH, R* and R′ are H, R⁵⁴ is the same as R⁴,R^(54′) is the same as R^(4′), R⁵⁵ is the same as R⁵, R⁵⁶ is the same asR⁶ and R⁵⁷ is the same as R⁷.

Metal complexes of formula

are more preferred, wherein X, R¹, R², R³, R⁴, R⁵ and L are as definedabove.

In said embodiment metal complexes of formula (Va-1), (Va-2), (Va-3) and(Va-4) are even more preferred, wherein the substituents have thefollowing meanings:

X is O.

R¹ is C₁-C₅alkyl, cyclopentyl, or cyclohexyl; preferably C₁-C₅alkyl,more preferably methyl, ethyl, isopropyl, or isobutyl.

R² is C₁-C₅alkyl, cyclopentyl, or cyclohexyl; preferably C₁-C₅alkyl,more preferably methyl, ethyl, isopropyl, or isobutyl.

R³ is H, C₁-C₅alkyl, cyclopentyl, or cyclohexyl; preferably H, methyl,ethyl, isopropyl, or isobutyl, more preferably H.

R⁴ and R⁵ are H, C₁-C₅alkyl, especially methyl, ethyl, isopropyl, orisobutyl; cyclopentyl, or cyclohexyl; preferably H.

In said embodiment metal complexes of formula (Va-1), (Va-2), (Va-3) and(Va-4) are most preferred, wherein the substituents have the followingmeanings:

X is O.

R¹ is C₁-C₅alkyl, more preferably methyl, ethyl, isopropyl, or isobutyl.

R² is C₁-C₅alkyl, more preferably methyl, ethyl, isopropyl, or isobutyl.

R³ is H, C₁-C₅alkyl, such as, for example, methyl, ethyl, isopropyl, orisobutyl; more preferably H.

R⁴ and R⁵ are H.

Examples of metal complexes of formula (Va-1), (Va-2), (Va-3) and (Va-4)are shown below.

Cpd. R¹ R² R⁴ = R⁵ Q-1 —CH₃ —CH₃ H Q-2 —CH₂CH₃ —CH₂CH₃ H Q-3 iso-propyliso-propyl H Q-4 iso-butyl iso-butyl H Q-5 neopentyl neopentyl H Q-6—CH₃ —CH₂CH₃ H Q-7

H Q-8

H Q-9 —CH₃ —CH₃ —CH₃ Q-10 —CH₂CH₃ —CH₂CH₃ —CH₃ Q-11 iso-propyliso-propyl —CH₃ Q-12 iso-butyl iso-butyl —CH₃ Q-13 neopentyl neopentyl—CH₃ Q-14 —CH₃ —CH₂CH₃ —CH₃ Q-15

—CH₃ Q-16

—CH₃ Q-17 —CH₃ —CH₃ —CH₂CH₃ Q-18 —CH₂CH₃ —CH₂CH₃ —CH₂CH₃ Q-19 iso-propyliso-propyl —CH₂CH₃ Q-20 iso-butyl iso-butyl —CH₂CH₃ Q-21 —CH₃ —CH₂CH₃—CH₂CH₃ Q-22 neopentyl neopentyl —CH₂CH₃ Q-23

—CH₂CH₃ Q-24

—CH₂CH₃ Q-25 —CH₃ —CH₃ iso-propyl Q-26 —CH₂CH₃ —CH₂CH₃ iso-propyl Q-27iso-propyl iso-propyl iso-propyl Q-28 iso-butyl iso-butyl iso-propylQ-29 neopentyl neopentyl iso-propyl Q-30 —CH₃ —CH₂CH₃ iso-propyl Q-31

iso-propyl Q-32

iso-propyl Q-33 —CH₃ —CH₃ iso-butyl Q-34 —CH₂CH₃ —CH₂CH₃ iso-butyl Q-35iso-propyl iso-propyl iso-butyl Q-36 iso-butyl iso-butyl iso-butyl Q-37neopentyl neopentyl iso-butyl Q-38 —CH₃ —CH₂CH₃ iso-butyl Q-39

iso-butyl Q-40

iso-butyl

Cpd. R¹ R² R⁴ = R⁵ R-1 —CH₃ —CH₃ H R-2 —CH₂CH₃ —CH₂CH₃ H R-3 iso-propyliso-propyl H R-4 iso-butyl iso-butyl H R-5 neopentyl neopentyl H R-6—CH₃ —CH₂CH₃ H R-7

H R-8

H R-9 —CH₃ —CH₃ —CH₃ R-10 —CH₂CH₃ —CH₂CH₃ —CH₃ R-11 iso-propyliso-propyl —CH₃ R-12 iso-butyl iso-butyl —CH₃ R-13 neopentyl neopentyl—CH₃ R-14 —CH₃ —CH₂CH₃ —CH₃ R-15

—CH₃ R-16

—CH₃ R-17 —CH₃ —CH₃ —CH₂CH₃ R-18 —CH₂CH₃ —CH₂CH₃ —CH₂CH₃ R-19 iso-propyliso-propyl —CH₂CH₃ R-20 iso-butyl iso-butyl —CH₂CH₃ R-21 —CH₃ —CH₂CH₃—CH₂CH₃ R-22 neopentyl neopentyl —CH₂CH₃ R-23

—CH₂CH₃ R-24

—CH₂CH₃ R-25 —CH₃ —CH₃ iso-propyl R-26 —CH₂CH₃ —CH₂CH₃ iso-propyl R-27iso-propyl iso-propyl iso-propyl R-28 iso-butyl iso-butyl iso-propylR-29 neopentyl neopentyl iso-propyl R-30 —CH₃ —CH₂CH₃ iso-propyl R-31

iso-propyl R-32

iso-propyl R-33 —CH₃ —CH₃ iso-butyl R-34 —CH₂CH₃ —CH₂CH₃ iso-butyl R-35iso-propyl iso-propyl iso-butyl R-36 iso-butyl iso-butyl iso-butyl R-37neopentyl neopentyl iso-butyl R-38 —CH₃ —CH₂CH₃ iso-butyl R-39

iso-butyl R-40

iso-butyl

Cpd. R² R³ R⁴ = R⁵ S-1 —CH₃ —CH₃ H S-2 —CH₂CH₃ —CH₂CH₃ H S-3 iso-propyliso-propyl H S-4 iso-butyl iso-butyl H S-5 neopentyl neopentyl H S-6—CH₃ —CH₂CH₃ H S-7

H S-8

H S-9 —CH₃ —CH₃ —CH₃ S-10 —CH₂CH₃ —CH₂CH₃ —CH₃ S-11 iso-propyliso-propyl —CH₃ S-12 iso-butyl iso-butyl —CH₃ S-13 neopentyl neopentyl—CH₃ S-14 —CH₃ —CH₂CH₃ —CH₃ S-15

—CH₃ S-16

—CH₃ S-17 —CH₃ —CH₃ —CH₂CH₃ S-18 —CH₂CH₃ —CH₂CH₃ —CH₂CH₃ S-19 iso-propyliso-propyl —CH₂CH₃ S-20 iso-butyl iso-butyl —CH₂CH₃ S-21 —CH₃ —CH₂CH₃—CH₂CH₃ S-22 neopentyl neopentyl —CH₂CH₃ S-23

—CH₂CH₃ S-24

—CH₂CH₃ S-25 —CH₃ —CH₃ iso-propyl S-26 —CH₂CH₃ —CH₂CH₃ iso-propyl S-27iso-propyl iso-propyl iso-propyl S-28 iso-butyl iso-butyl iso-propylS-29 neopentyl neopentyl iso-propyl S-30 —CH₃ —CH₂CH₃ iso-propyl S-31

iso-propyl S-32

iso-propyl S-33 —CH₃ —CH₃ iso-butyl S-34 —CH₂CH₃ —CH₂CH₃ iso-butyl S-35iso-propyl iso-propyl iso-butyl S-36 iso-butyl iso-butyl iso-butyl S-37neopentyl neopentyl iso-butyl S-38 —CH₃ —CH₂CH₃ iso-butyl S-39

iso-butyl S-40

iso-butyl

Cpd. R² R³ R⁴ = R⁵ T-1 —CH₃ —CH₃ H T-2 —CH₂CH₃ —CH₂CH₃ H T-3 iso-propyliso-propyl H T-4 iso-butyl iso-butyl H T-5 neopentyl neopentyl H T-6—CH₃ —CH₂CH₃ H T-7

H T-8

H T-9 —CH₃ —CH₃ —CH₃ T-10 —CH₂CH₃ —CH₂CH₃ —CH₃ T-11 iso-propyliso-propyl —CH₃ T-12 iso-butyl iso-butyl —CH₃ T-13 neopentyl neopentyl—CH₃ T-14 —CH₃ —CH₂CH₃ —CH₃ T-15

—CH₃ T-16

—CH₃ T-17 —CH₃ —CH₃ —CH₂CH₃ T-18 —CH₂CH₃ —CH₂CH₃ —CH₂CH₃ T-19 iso-propyliso-propyl —CH₂CH₃ T-20 iso-butyl iso-butyl —CH₂CH₃ T-21 —CH₃ —CH₂CH₃—CH₂CH₃ T-22 neopentyl neopentyl —CH₂CH₃ T-23

—CH₂CH₃ T-24

—CH₂CH₃ T-25 —CH₃ —CH₃ iso-propyl T-26 —CH₂CH₃ —CH₂CH₃ iso-propyl T-27iso-propyl iso-propyl iso-propyl T-28 iso-butyl iso-butyl iso-propylT-29 neopentyl neopentyl iso-propyl T-30 —CH₃ —CH₂CH₃ iso-propyl T-31

iso-propyl T-32

iso-propyl T-33 —CH₃ —CH₃ iso-butyl T-34 —CH₂CH₃ —CH₂CH₃ iso-butyl T-35iso-propyl iso-propyl iso-butyl T-36 iso-butyl iso-butyl iso-butyl T-37neopentyl neopentyl iso-butyl T-38 —CH₃ —CH₂CH₃ iso-butyl T-39

iso-butyl T-40

iso-butyl

Among the above metal carbene-complexes Q-1 to Q-40, R-1 to R-40, S-1 toS-40 and T-1 to T-40 the metal carbene-complexes Q-1 to Q-8, R-1 to R-8,S-1 to S-8, and T-1 to T-8 are preferred.

The at present most preferred metal carbene-complexes are metalcarbene-complexes A-1 to A-14, C-1 to C-22, C-125 to C-130, C-161 toC-163, I-1 to I-14, J-1 to J-22 and J-111 to J-116. Among these metalcarbene-complexes metal carbene-complexes A-2, A-3, A-4, A-6, A-14,C-126, C-127 and C-128 are even more preferred.

In the alkyl groups and aryl groups mentioned above one or more hydrogenatoms may be substituted by deuterium atoms.

A process for preparing a metal-carbene complexes of formula

wherein M is Pt and m is 2; or M is Ir and m is 3, R is a group offormula

may comprise reacting a compound of formula

with a compound of formula

whereinX¹ is Cl, Br, or I, especially Br;Y is —B(OH)₂, —B(OY¹)₂,

wherein Y¹ is independently in each occurrence a C₁-C₁₀alkyl group andY² is independently in each occurrence a C₂-C₁₀alkylene group, such as—CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹Y¹²—, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷,Y⁸, Y⁹, Y¹⁰, Y¹¹ and Y¹² are independently of each other hydrogen, or aC₁-C₁₀alkyl group, especially —C(CH₃)₂C(CH₃)₂—, —CH₂C(CH₃)₂CH₂—, or—C(CH₃)₂CH₂C(CH₃)₂—, and Y¹³ and Y¹⁴ are independently of each otherhydrogen, or a C₁-C₁₀alkyl group;—SnR³⁰⁷R³⁰⁸R³⁰⁹, wherein R³⁰⁷, R³⁰⁸ and R³⁰⁹ are identical or differentand are H or C₁-C₆alkyl, wherein two radicals optionally form a commonring and these radicals are optionally branched or unbranched;ZnR³¹⁰R³¹¹, wherein R³¹⁰ is halogen and R³¹¹ is a C₁-C₁₀alkyl group, aC₆-C₁₂aryl group, or C₁-C₁₀alkenyl group; orSiR³¹²R³¹³R³¹⁴, wherein R³¹², R³¹³ and R³¹⁴ are identical or differentand are halogen, or C₁-C₆alkyl; andR, R′, R¹, R², R³, R^(3′), R^(3″), R⁴, R^(4′), R⁵, R⁶ and R⁷ are asdefined above.

The process is also suitable for producing metal-carbene complexes offormula process for preparing a metal-carbene complexes of formula

starting from

respectively.

Preferred reactions for the introduction of aryl substituents on thecompound of formula (X) are in general metal catalyzed reactions andmore specifically Suzuki, Ullmann, Negishi, Heck, Stille and Kumadacoupling reactions (J. Hassan et al., Chemical Reviews 102 (2002) 5; L.Ackermann: “Modern Arylation Methods” (Ed.: L. Ackermann), Wiley-VCH,Weinheim, 2009).

Advantageously, the metal-carbene complexes of formula (I) can besynthesized by one of the following coupling reactions:

i) Negishi coupling reaction using a compound of formula (XII), whereinY is ZnR³¹⁰R³¹¹ wherein R³¹⁰ is halogen and R³¹¹ is a C₁-C₁₀alkyl group,a C₆-C₁₂aryl group, or C₁-C₁₀alkenyl group. Reference is, for example,made to B. Vilas et al., Chem. Soc. Rev., 38 (2009) 1598-1607.ii) Stille coupling reaction using a compound of formula (XII), whereinY is —SnR³⁰⁷R³⁰⁸R³⁰⁹, wherein R³⁰⁷, R³⁰⁸ and R³⁰⁹ are identical ordifferent and are H or C₁-C₆alkyl, wherein two radicals optionally forma common ring and these radicals are optionally branched or unbranched.Reference is, for example, made to J. K. Stille, Angew. Chem. 98 (1986)504-519; P. Espinet et al., Angew. Chem. Int. Ed., 43 (2004) 4704-4734.iii) Hiyama coupling reaction using a compound of formula (XII), whereinY is SiR³¹²R³¹³R³¹⁴, wherein R³¹², R³¹³ and R³¹⁴ are identical ordifferent and are halogen, or C₁-C₆alkyl. Reference is, for example,made to T. Hiyama et al., Pure Appl. Chem. 66 (1994) 1471-1478 and T.Hiyama et al., Synlett (1991) 845-853; andiv) Suzuki coupling reaction using a compound of formula

wherein Y is —B(OH)₂, —B(OY¹)₂,

wherein Y¹ is independently in each occurrence a C₁-C₁₀alkyl group andY² is independently in each occurrence a C₂-C₁₀alkylene group, such as—CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹Y¹²—, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷Y⁸,Y⁹, Y¹⁰, Y¹¹ and Y¹² are independently of each other hydrogen, or aC₁-C₁₀alkyl group, especially —C(CH₃)₂C(CH₃)₂—, —CH₂C(CH₃)₂CH₂—, or—C(CH₃)₂CH₂C(CH₃)₂—, and Y¹³ and Y¹⁴ are independently of each otherhydrogen, or a C₁-C₁₀alkyl group. Reference is, for example, made to A.Suzuki et al., Chemical Reviews 95 (1995) 2457-2483, “Suzuki in ModemArene Chemistry” (Ed.: D. Astruc), Wiley-VCH, Weinheim, 2002, pp.53-106. More preferably Suzuki and Negishi coupling reactions are used.Suzuki type reactions are most preferred.

Preferably, the Suzuki reaction of compound (X) with compound (XII) iscarried out in presence of

a) a catalyst/ligand system comprising a palladium catalyst and anorganic phosphine or phosphonium compound,b) a base,c) a solvent or a mixture of solvents.

The organic solvent is usually an aromatic hydrocarbon, a linear,branched, or cyclic ether, or a usual polar organic solvent, such asbenzene, toluene, xylene, tetrahydrofurane, or dioxane, or mixturesthereof. If desired, water can be added to the organic reaction medium,in which case, depending on the organic solvent used, the reaction canbe carried out in a single phase or in a two-phase mixture.

Usually, the amount of the solvent is chosen in the range of from 1 to10 l per mol of boronic acid derivative.

Also preferred, the reaction is carried out under an inert atmospheresuch as nitrogen, or argon.

Further, it is preferred to carry out the reaction in the presence of anaqueous base, such as an alkali metal hydroxide, metal phosphate, orcarbonate such as NaOH, KOH, K₃PO₄, Na₂CO₃, K₂CO₃, or Cs₂CO₃.

Organic bases, such as, for example, tetraalkylammonium hydroxide, andphase transfer catalysts, such as, for example TBAB, can promote theactivity of the boron (see, for example, Leadbeater & Marco; Angew.Chem. Int. Ed. Eng. 42 (2003) 1407 and references cited therein).

Usually, the molar ratio of the base to boronic acid or boronic esterderivative is chosen in the range of from 0.5:1 to 50:1, very especiallyin the range of 1:1 to 5:1.

Generally, the reaction temperature is chosen in the range of from 40 to180° C., preferably under reflux conditions.

Generally, the reaction time is chosen in the range of from 0.5 to 80hours, preferably from 2 hours to 60 hours.

In a preferred embodiment a usual catalyst for coupling reactions or forpolycondensation reactions is used, preferably Pd-based, which isdescribed in WO2007/101820. The palladium compound is added in a ratioof from 1:10000 to 1:50, preferably from 1:5000 to 1:200, based on thenumber of bonds to be closed. Preference is given, for example, to theuse of palladium(II) salts such as PdOAc₂ or Pd₂dba₃ and to the additionof ligands selected from the group consisting of

wherein

The ligand is added in a ratio of from 1:1 to 1:10, based on Pd. Alsopreferred, the catalyst is added as in solution or suspension.Preferably, an appropriate organic solvent such as the ones describedabove, preferably benzene, toluene, xylene, THF, dioxane, morepreferably toluene, or mixtures thereof, is used. The amount of solventusually is chosen in the range of from 1 to 10 l per mol of boronic acidderivative.

Other variations of reaction conditions are given by T. I. Wallow and B.M. Novak in J. Org. Chem. 59 (1994) 5034-5037; and M. Remmers, M.Schulze, G. Wegner in Macromol. Rapid Commun. 17 (1996) 239-252 and G.A. Molander und B. Canturk, Angew. Chem., 121 (2009) 9404-9425. Thefollowing reaction systems are preferred:

i) aryl boronic acid, tris(dibenzylideneacetone) dipalladium(0), SPhos(Dicyclohexylphosphino-2′,6′-dimethoxybiphenyl), tripotassium phosphate(solvent toluene/water mixture);ii) aryl boronic acid, bis(tri-t-butylphosphin)palladium(0)(Pd[P(tBu)₃]2), sodium hydroxide (solvent toluene/dioxane/watermixture); andiii) aryl boronic acid, palladium acetate (Pd(OAc)₂), SPhos(Dicyclohexylphosphino-2′,6′-dimethoxybiphenyl), tripotassium phosphate(o-xylene mixture).

The compound of formula (X) can be obtained by reacting a compound offormula

with a halogenating agent, wherein R′, R⁴, R^(4′), R⁵, R⁶ and R⁷ are asdefined in above. The halogenation can be performed by methods known tothose skilled in the art.

Halogenating agents according to the invention are the halogens X₂ orthe interhalogens X-X and a base in a ratio of from 1:1 to 1:100 andoptionally a Lewis acid in a ratio (halogen to Lewis acid) of from 1:0.1to 1:0.0001, for example chlorine, bromine or iodine, or chlorinefluoride, bromine fluoride, iodine fluoride, bromine chloride, iodinechloride or iodine bromide, in combination with organic bases such asamines, for example triethylamine, tri-n-butylamine,diisopropylethylamine, morpholine, N-methylmorpholine and pyridine, orsalts of carboxylic acids such as sodium acetate, sodium propionate,sodium benzoate, or inorganic bases such as sodium or potassiumphosphate or hydrogenphosphate, potassium or sodium hydrogencarbonate,potassium or sodium carbonate, or else organic bromine complexes such aspyridinium perbromide, optionally each in combination with a Lewis acid,e.g. boron trifluoride, boron trifluoride etherate, boron trichloride,boron tribromide, boron triiodide, aluminum trichloride, aluminumtribromide, aluminum triiodide, iron(III) chloride, iron(III)bromide,zinc(II)chloride, zinc(II)bromide, tin(IV)chloride, tin(IV)bromide,phosphorus pentachloride, arsenic pentachloride and antimonypentachloride are used.

Further halogenating agents according to the invention are organic N—Xcompounds, such as1-(chloromethyl)-4-fluoro-1,4-diazoniabicyclo[2.2.2]octanebis(tetrafluoroborate), or N-halocarboxamides such as N-chloro-,N-bromo- and N-iodoacetamide, N-chloro-, N-bromo- andN-iodopropionamide, N-chloro-, N-bromo- and N-iodobenzamide, orN-halocarboximides such as N-chloro-, N-bromo- and N-iodosuccinimide,N-chloro-, N-bromo- and N-iodophthalimide, or N,N-dihalohydantoins, suchas 1,3-dibromo-5,5-dimethylhydantoin,1,3-dichloro-5,5-dimethylhydantoin, 1,3-diiodo-5,5-dimethylhydantoin orN-dihalosulfonamides such as, benzenesulfo-N-dibromamide, orN-halosulfonamide salts such as chloramine B or T. In the case of thesehalogenating agents, the additive use of Lewis acids, as listed above,for example, may likewise be advantageous.

Preferred halogenating agents N-halocarboxamides such as N-chloro-,N-bromo- and N-iodosuccinimide, N-chloro-, N-bromo- andN-iodophthalimide, or N,N-dihalohydantoins, such as1,3-dibromo-5,5-dimethylhydantoin, 1,3-dichloro-5,5-dimethylhydantoinand 1,3-diiodo-5,5-dimethylhydantoin.

In the process according to the invention, a stoichiometric ratio or anexcess of the halogenating agent based on the content of active halogen,to the compounds (XI) is used, and can lead selectively to the compounds(X). Preferably a stoichiometric ratio up to a ratio of 2:1 of thehalogenating agent based on the content of active halogen to thecompounds (XI) is used. More preferably a stoichiometric ratio is used.

Reaction media according to the invention are protic or aprotic,halogen-free or halogenated solvents, for example alcohols such asmethanol, ethanol, propanol, butanol, polyhydric alcohols such asethylene glycol, propyleneglycol, nitriles such as acetonitrile,propionitrile or benzonitrile, ethers such as diethyl ether THF ordioxane, aromatic hydrocarbons such as benzonitrile, nitrobenzene orchlorobenzene, N,N-dialkylamides such as dimethylformamide,methylacetamide or N-methylpyrroldinone, sulfoxides, such as dimethylsulfoxide, sulfones such as dimethylsulfone or sulfolane, halogenatedhydrocarbons such as dichloromethane, trichloromethanen,1,1-dichloroethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane.Preference is given to aromatic or chlorinated solvents.

According to the invention, the concentration of the compound of formula(XI) is in the range from 0.0005 mol/I to 2 mol/I, more preferably inthe range from 0.002 mol/I to 0.1 mol/l.

According to the invention, the compound of formula (XI) may bedissolved or suspended in the reaction medium.

According to the invention, the reaction is carried out in thetemperature range from −78° C. to 150° C., preferably at from 0° C. to80° C., more preferably at from 0° C. to 40° C.

According to the invention, the reaction is carried out within from 1 hto 100 hours, preferably within from 3 h to 60 h.

Brominating in the 3 position of the cyclometallating N-aryl group ofthe diazabenzimidazole carbene ligand can be, for example, accomplishedby reaction of the compound of formula (X) with N-bromosuccinimide indichloromethane.

Iodinating in the 3 position of the cyclometallating N-aryl group of thediazabenzimidazole carbene ligand can be, for example, accomplished byreaction of the compound of formula (X) with N-iodosuccinimide indichloromethane.

Carbene complexes which are suitable as starting material (XI) are, forexample, specified in the following publications: WO2011/073149,US2012/0305894, WO2012/121936, and WO2012/170461.

The present invention also relates to a process for preparing theinventive metal-carbene complexes comprising one, two or three,preferably three in the case of Ir and preferably one in the case of Pt,bidentate ligands of formula

by contacting suitable compounds comprising Ir or Pt with theappropriate ligands or ligand precursors.

In one embodiment of the process according to the invention, a suitablecompound comprising iridium or platinum, preferably iridium, andappropriate carbene ligands, preferably in deprotonated form as the freecarbene or in the form of a protected carbene, for example as thesilver-carbene complex, are contacted.

The present invention therefore relates—in one embodiment—to a processaccording to the invention wherein the ligand precursor used is acorresponding Ag-carbene complex.

In a further preferred embodiment of the process according to theinvention, the ligand precursors used are organic compounds which arereacted with suitable Ir or Pt comprising compounds. The carbene can bereleased from precursors of the carbene ligands by removing volatilesubstances, for example lower alcohols such as methanol or ethanol, forexample at elevated temperature and/or under reduced pressure and/orusing molecular sieves which bind the alcohol molecules eliminated.Corresponding processes are known to those skilled in the art.

The present invention also relates to the process according to theinvention wherein the ligand precursor used is a compound of the generalformula

wherein R, R′, R⁴, R^(4′), R⁵, R⁶ and R⁷ are as defined above, andR″ is SiR¹³R¹⁴R¹⁵, aryl, heteroaryl, alkyl, cycloalkyl orheterocycloalkyl, whereinR¹³, R¹⁴ and R¹⁵ are independently of each other aryl, heteroaryl,alkyl, cycloalkyl or heterocycloalkyl.

In a particularly preferred embodiment, R″ is alkyl, especiallyC₁-C₂₀alkyl, preferably C₁-C₁₀alkyl, more preferably C₁-C₈alkyl, forexample methyl, ethyl, propyl such as n-propyl, isopropyl, butyl such asn-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl or octyl.

R″ in the compound of the general formula (XX) is most preferably methylor ethyl.

Compounds of the general formula (XX) are generally obtainable byprocesses known to those skilled in the art. Compounds of the generalformula (XX) can be obtained for example by reacting compounds of thegeneral formula (XXIa)

or the corresponding Cl or BF₄ salt of formula

wherein X is Cl or BF₄, with compounds of the general formula HC(OR″)₃(XXII), or by reacting compounds of the general formula (XXIa) in afirst step with Vilsmeier reagent ((chloromethylene)dimethylammoniumchloride) and a sodium salt selected from NaBF₄, NaCl, NaBr or NaI toobtain a compound of formula (XXIc)

wherein X is BF₄, Cl, Br or I and in a second step with R″OH or M″OR″,wherein M″ is an alkali metal salt, preferably Na, wherein R, R′, R⁴,R^(4′), R⁵, R⁶ and R⁷ are as defined above and the metal is Ir or Pt,comprising one, two or three bidentate ligands of formula (D).

This preparation of the compounds of the general formula (XX) can beeffected in the presence or in the absence of a solvent. Suitablesolvents are specified below. In one preferred embodiment, the compoundsof the general formula (XX) are prepared in substance, or the compoundof the general formula (XXII) is added in an excess, such that itfunctions as a solvent.

Compounds of the general formulae (XXI) and (XXII) are commerciallyavailable and/or obtainable by processes known to those skilled in theart; for example, compounds of the general formula (XXI) are obtainableby reacting the appropriate chlorides with the appropriate amines.

The compounds of the general formula (XX) are prepared generally at atemperature of 10 to 150° C., preferably 40 to 120° C., more preferably60 to 110° C.

The reaction time is generally 2 to 48 hours, preferably 6 to 24 hours,more preferably 8 to 16 hours.

After the reaction has ended, the desired product can be isolated andpurified by customary processes known to those skilled in the art, forexample filtration, recrystallization, column chromatography, etc.

Appropriate compounds, especially complexes, comprising Ir or Pt,preferably iridium, are known to those skilled in the art. Particularlysuitable compounds comprising platinum or iridium comprise, for example,ligands such as halides, preferably chloride, 1,5-cyclooctadiene (COD),cyclooctene (COE), phosphines, cyanides, alkoxides, pseudohalides and/oralkyl.

Particularly preferred complexes comprising the appropriate metal,especially iridium, are selected from the group consisting of[Ir(COD)Cl]₂, [Ir(COE)₂Cl]₂IrCl₃xH₂O, Ir(acac)₃, Ir(COD)₂BF₄,Ir(COD)₂BARF (BARF=tetrakis[3,5-bis(trifluoromethyl)phenyl]borate)),Pt(COD)Cl₂, Pt(acac)₂, [Pt(C₆H₁₀)Cl₂]2, K₂PtCl₆, Pt(pyridine)₂Cl₂,[PtMe₂(SMe₂)]₂, Pt(SMe₂)₂Cl₂, Pt(SEt₂)₂Cl₂, Pt(phenanthroline)C₂,Pt(NH₃)₂Cl₂ and mixtures thereof.

The carbene ligand precursors are deprotonated, preferably before thereaction, for example, by basic compounds known to those skilled in theart, for example basic metalates, basic metal acetates, acetylacetonatesor alkoxides, or bases such as KOtBu, NaOtBu, LiOtBu, NaH, silylamides,Ag₂O and phosphazene bases. Particular preference is given todeprotonating with Ag₂O to obtain the corresponding Ag-carbene, which isreacted with the compound comprising M to give the inventive complexes.

Particularly preferably, the carbene can be released from precursors ofthe carbene ligands by removing volatile substances, for example loweralcohols.

The process according to the invention for preparing the metal-carbenecomplexes, wherein the metal is Ir or Pt, comprising one, two or threebidentate ligands of formula (D) according to the present inventionusing the compounds of the general formula (XX) has the advantage thatthe compounds of the general formula (XX) are stable intermediates whichcan be handled readily and can be isolated under standard laboratoryconditions. In addition, the compounds of the general formula (XX) aresoluble in customary organic solvents, such that the preparation of theinventive metal-carbene complexes, wherein the metal is Ir or Pt,comprising one, two or three bidentate ligands of formula (D) inhomogeneous solution is possible, such that a workup of the desiredproduct, i.e. of the metal-carbene complexes, wherein the metal is Ir orPt, comprising one, two or three bidentate ligands of formula (D) ismore readily possible, for example for isolation and/or purification.

The contacting is preferably effected in a solvent. Suitable solventsare known per se to those skilled in the art and are preferably selectedfrom the group consisting of aromatic or aliphatic solvents, for examplebenzene, toluene, xylene or mesitylene, cyclic or acyclic ethers, forexample dioxane or THF, alcohols, esters, amides, ketones, nitriles,halogenated compounds and mixtures thereof. Particularly preferredsolvents are toluene, xylenes, mesitylene and dioxane.

The molar ratio of metal-noncarbene complex used to carbene ligandprecursor used is generally 1:10 to 10:1, preferably 1:1 to 1:6, morepreferably 1:2 to 1:5.

The contacting is generally effected at a temperature of 20 to 200° C.,preferably 50 to 150° C., more preferably 60 to 150° C.

The reaction time depends on the desired carbene complex and isgenerally 0.02 to 50 hours, preferably 0.1 to 24 hours, more preferably1 to 24 hours.

The metal-carbene complexes, wherein the metal is Ir or Pt, comprisingone, two or three bidentate ligands of formula (D) obtained after thereaction can optionally be purified by processes known to those skilledin the art, for example washing, crystallization or chromatography, andoptionally isomerized under conditions likewise known to those skilledin the art, for example with acid mediation, thermally orphotochemically.

Suitable processes for preparing the metal-carbene complex comprisingone, two or three, preferably three, bidentate ligands of formula (D)are for example mentioned in WO 2011/073149 and EP13174779.

The resulting complexes may yield different isomers that can beseparated or converted into a form with a major isomer by isomerizationof the mixture.

The inventive metal-carbene complexes can be used in electronic devices,especially OLEDs (Organic Light-Emitting Diodes), for example, asemitter, matrix material, charge transport material and/or charge orexciton blocker.

The inventive metal-carbene complexes are generally notable for improveddevice performance such as high external quantum efficiency, highluminous efficacy and low voltage, blue emission, decreased lifetime ofthe luminescence t (higher radiation rate k_(rad)), reduced color-shift(e.g. CIE-y shift) with increasing doping concentration, or long devicelifetime and/or excellent thermal stability.

The inventive metal-carbene complexes are therefore suitable withparticular preference as emitter material in OLEDs.

The inventive metal-carbene complexes can be used in electronic devices,for example organic electronic devices selected from switching elementssuch as organic light-emitting diodes (OLEDs), organic photovoltaiccells (OPVs), organic field-effect transistors (OFETs) andlight-emitting electrochemical cells (LEECs), preference being given tousing the metal-carbene complexes of the formula (I) in OLEDs.

The inventive metal-carbene complex is preferably a compound of formula(IIIa) to (IIIe), especially a compound of formula (IIIa-1) to (IIIe-1),very especially a compound (A-1) to (A-70) and (C-1) to (C-110), (C-125)to (C-154), and (C-161) to (C-163), wherein those compounds areparticularly preferred, wherein R⁴ and R⁵ are H, i.e. compounds (A-1) to(A-14), (C-1) to (C-22), (C-125) to (C-130) and (C-161) to (C-163).

In a preferred embodiment, the organic electronic device is an OLEDcomprising a light-emitting layer comprising at least one inventivemetal-carbene complex.

In addition, the inventive metal-carbene complexes can be used as matrixmaterial, charge transport material, especially hole transport material,and/or charge blocker.

The inventive metal-carbene complexes are preferably used as an emitterand/or charge transport material and/or matrix material, more preferablyas an emitter.

Particular properties of the inventive metal-carbene complexes areparticularly good efficiencies, good CIE color loci and long lifetimeswhen used in OLEDs.

The present application therefore further provides an OLED comprising atleast one inventive metal-carbene complex. The inventive metal-carbenecomplex is used in the OLED preferably as an emitter, matrix material,charge transport material, especially hole transport material, and/orcharge blocker, more preferably as an emitter and/or hole transportmaterial, most preferably as an emitter.

The present application also provides for the use of the inventivemetal-carbene complexes in OLEDs, preferably as an emitter, matrixmaterial, charge transport material, especially hole transport material,and/or charge blocker, more preferably as an emitter and/or holetransport material, most preferably as an emitter.

Organic light-emitting diodes are in principle formed from a pluralityof layers, e.g.:

(a) an anode,(b) optionally a hole injection layer,(c) optionally a hole transport layer,(d) optionally an exciton blocking layer(e) a light-emitting layer, comprising(f) optionally a hole/exciton blocking layer(g) optionally an electron transport layer,(h) optionally an electron injection layer, and(i) a cathode.

It is, however, also possible that the OLED does not have all of thelayers mentioned; for example, an OLED comprising layers (a) (anode),(e) (light-emitting layer) and (i) (cathode) is likewise suitable, inwhich case the functions of layers (c) (hole-transport layer) and (g)(electron-transport layer) are assumed by the adjoining layers. OLEDshaving layers (a), (c), (e), (g) and (i) or (a), (c), (e) and (i) orlayers (a), (e), (g) and (i) are likewise suitable.

The inventive metal-carbene complexes are preferably used as emittermolecules and/or matrix materials in the light-emitting layer (e). Theinventive metal-carbene complexes may—in addition to use as emittermolecules and/or matrix materials in the light-emitting layer (e) orinstead of use in the light-emitting layer—also be used as a chargetransport material in the hole-transport layer (c) or in theelectron-transport layer (g) and/or as a charge blocker, preferencebeing given to use as a charge transport material in the hole-transportlayer (c) (hole transport material).

The present application therefore further provides a light-emittinglayer comprising at least one of the inventive metal-carbene complexes,preferably as emitter material and/or matrix material, more preferablyas emitter material. Preferred inventive metal-carbene complexes havealready been specified above.

The light-emitting layer comprises preferably at least one metal-carbenecomplex according to the invention, especially used as emissivematerial, and a host material.

In a further embodiment, the present invention relates to alight-emitting layer consisting of at least one inventive metal-carbenecomplex.

The inventive metal-carbene complexes used in accordance with theinvention may be present in the light-emitting layer in substance, i.e.without further additions. However, it is also possible that, inaddition to the metal-carbene complexes used in accordance with theinvention, further compounds are present in the light-emitting layer. Inaddition, a diluent material (matrix material) may be used. This diluentmaterial may be a polymer, for example poly(N-vinylcarbazole) orpolysilane. The diluent material may, however, likewise be a smallmolecule, for example 4,4′-N,N′-dicarbazolebiphenyl (CDP) or tertiaryaromatic amines. When a diluent material is used, the proportion of theinventive metal-carbene complexes in the light-emitting layer isgenerally less than 40% by weight, preferably 3 to 30% by weight. Theinventive metal-carbene complexes are preferably used in a matrix.

The light-emitting layer thus preferably comprises at least oneinventive metal-carbene complex and at least one matrix material.

Preferred further phosphosphorescence emitters are carbene complexes.Carbene complexes which are suitable phosphorescent blue emitters arespecified in the following publications: WO 2006/056418 A2, WO2005/113704, WO 2007/115970, WO 2007/115981, WO 2008/000727,WO2009050281, WO2009050290, WO2011051404, US2011/057559 WO2011/073149,WO2012/121936A2, US2012/0305894A1, WO2012170571, WO2012170461, WO2012170463, WO2006121811, WO2007095118, WO2008156879, WO2008156879,WO2010068876, US20110057559, WO2011106344, US20110233528, WO2012048266and WO2012172482.

Suitable matrix materials are in principle the materials specifiedhereinafter as hole and electron transport materials, and also carbencomplexes, for example, the inventive metal-carbene complexes, or thecarbene complexes mentioned in WO 2005/019373.

Particularly suitable are carbazole derivatives, for example4,4′-bis(carbazol-9-yl)-2,2′-dimethylbiphenyl (CDBP),4,4′-bis(carbazol-9-yl)biphenyl (CBP), 1,3-bis(N-carbazolyl)benzene(mCP), and the matrix materials specified in the following applications:WO2008/034758, WO2009/003919.

Further suitable matrix materials, which may be small molecules or(co)polymers of the small molecules mentioned, are specified in thefollowing publications: WO2007108459 (H-1 to H-37), preferably H-20 toH-22 and H-32 to H-37, most preferably H-20, H-32, H-36, H-37,WO2008035571 A1 (Host 1 to Host 6), JP2010135467 (compounds 1 to 46 andHost-1 to Host-39 and Host-43), WO2009008100 compounds No. 1 to No. 67,preferably No. 3, No. 4, No. 7 to No. 12, No. 55, No. 59, No. 63 to No.67, more preferably No. 4, No. 8 to No. 12, No. 55, No. 59, No. 64, No.65, and No. 67, WO2009008099 compounds No. 1 to No. 110, WO2008140114compounds 1-1 to 1-50, WO2008090912 compounds OC-7 to OC-36 and thepolymers of Mo-42 to Mo-51, JP2008084913 H-1 to H-70, WO2007077810compounds 1 to 44, preferably 1, 2, 4-6, 8, 19-22, 26, 28-30, 32, 36,39-44, WO201001830 the polymers of monomers 1-1 to 1-9, preferably of1-3, 1-7, and 1-9, WO2008029729 the (polymers of) compounds 1-1 to 1-36,WO20100443342 HS-1 to HS-101 and BH-1 to BH-17, preferably BH-1 toBH-17, JP2009182298 the (co)polymers based on the monomers 1 to 75,JP2009170764, JP2009135183 the (co)polymers based on the monomers 1-14,WO2009063757 preferably the (co)polymers based on the monomers 1-1 to1-26, WO2008146838 the compounds a-1 to a-43 and 1-1 to 1-46,JP2008207520 the (co)polymers based on the monomers 1-1 to 1-26,JP2008066569 the (co)polymers based on the monomers 1-1 to 1-16,WO2008029652 the (co)polymers based on the monomers 1-1 to 1-52,WO2007114244 the (co)polymers based on the monomers 1-1 to 1-18,JP2010040830 the compounds HA-1 to HA-20, HB-1 to HB-16, HC-1 to HC-23and the (co)polymers based on the monomers HD-1 to HD-12, JP2009021336,WO2010090077 the compounds 1 to 55, WO2010079678 the compounds H1 toH42, WO2010067746, WO2010044342 the compounds HS-1 to HS-101 and Poly-1to Poly-4, JP2010114180 the compounds PH-1 to PH-36, US2009284138 thecompounds 1 to 111 and H1 to H71, WO2008072596 the compounds 1 to 45,JP2010021336 the compounds H-1 to H-38, preferably H-1, WO2010004877 thecompounds H-1 to H-60, JP2009267255 the compounds 1-1 to 1-105,WO2009104488 the compounds 1-1 to 1-38, WO2009086028, US2009153034,US2009134784, WO2009084413 the compounds 2-1 to 2-56, JP2009114369 thecompounds 2-1 to 2-40, JP2009114370 the compounds 1 to 67, WO2009060742the compounds 2-1 to 2-56, WO2009060757 the compounds 1-1 to 1-76,WO2009060780 the compounds 1-1 to 1-70, WO2009060779 the compounds 1-1to 1-42, WO2008156105 the compounds 1 to 54, JP2009059767 the compounds1 to 20, JP2008074939 the compounds 1 to 256, JP2008021687 the compounds1 to 50, WO2007119816 the compounds 1 to 37, WO2010087222 the compoundsH-1 to H-31, WO2010095564 the compounds HOST-1 to HOST-61, WO2007108362,WO2009003898, WO2009003919, WO2010040777, US2007224446, WO06128800,WO2012014621, WO2012105310, WO2012/130709 and European patentapplications EP12175635.7 and EP12185230.5, EP12191408.9 (in particularpage 25 to 29 of EP12191408.9), WO2012048266, WO2012145173,WO2012162325, and EP2551932.

In a particularly preferred embodiment, one or more compounds of thegeneral formula (X) specified hereinafter are used as matrix material.

wherein

X is NR, S, O or PR;

R is aryl, heteroaryl, alkyl, cycloalkyl, or heterocycloalkyl;A²⁰⁰ is —NR²⁰⁶R²⁰⁷, —P(O)R²⁰⁸R²⁰⁹, —PR²¹⁰R²¹¹, —S(O)₂R²¹², —S(O)R²¹³,—SR²¹⁴, or —OR²¹⁵;R²²¹, R²²² and R²²³ are independently of each other aryl, heteroaryl,alkyl, cycloalkyl, or heterocycloalkyl, wherein at least on of thegroups R²²¹, R²²², or R²²³ is aryl, or heteroaryl;R²²⁴ and R²²⁵ are independently of each other alkyl, cycloalkyl,heterocycloalkyl, aryl, heteroaryl, a group A¹, or a group having donor,or acceptor characteristics;n2 and m1 are independently of each other 0, 1, 2, or 3;R²⁰⁶, R²⁰⁷ form together with the nitrogen atom a cyclic residue having3 to 10 ring atoms, which can be unsubstituted, or which can besubstituted with one, or more substituents selected from alkyl,cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group having donor,or acceptor characteristics; and/or which can be annulated with one, ormore further cyclic residues having 3 to 10 ring atoms, wherein theannulated residues can be unsubstituted, or can be substituted with one,or more substituents selected from alkyl, cycloalkyl, heterocycloalkyl,aryl, heteroaryl and a group having donor, or acceptor characteristics;andR²⁰⁸, R²⁰⁹, R²¹⁰, R²¹¹, R²¹², R²¹³, R²¹⁴ und R²¹⁵ are independently ofeach other aryl, heteroaryl, alkyl, cycloalkyl, or heterocycloalkyl.

Compounds of formula (X) and their preparation processes, such as, forexample,

are described in WO2010/079051 (in particular pages on 19 to 26 and intables on pages 27 to 34, pages 35 to 37 and pages 42 to 43).

Additional host materials on basis of dibenzofurane are, for example,described in US 2009066226, EP1885818, EP1970976, EP1998388 andEP2034538. Examples of particularly preferred host materials are shownbelow:

In the above-mentioned compounds T is O, or S, preferably O. If T occursmore than one time in a molecule, all groups T have the same meaning.

The more preferred host compounds are shown below:

as well as the host materials published in WO2012048266, WO2012145173,WO2012162325, and EP2551932.

The most preferred host compounds are shown below:

In a preferred embodiment, the light-emitting layer is formed from 2 to40% by weight, preferably 5 to 35% by weight, of at least one of theinventive metal carben complexes and 60 to 98% by weight, preferably 65to 95% by weight, of at least one of the aforementioned matrixmaterials, where the sum total of the emitter material and of the matrixmaterial adds up to 100% by weight.

-   In particularly preferred embodiment, the light-emitting layer    comprises a matrix material, such as, for example, compound (SH-1),    or (SH-2) and two carbene complexes, such as for example, compound    (A-17) and

-    said embodiment, the light-emitting layer is formed from 2 to 40%    by weight, preferably 5 to 35% by weight, of (A-17 and 60 to 98% by    weight, preferably 65 to 95% by weight, of SH-1 and Ir(DPBIC)₃,    where the sum total of the carben complexes and SH-1 adds up to 100%    by weight.

Suitable metal complexes for use as matrix material and/or hole/excitonblocker material and/or electron/exciton blocker material and/or holeinjection material and/or electron injection material and/or holetransport material and/or electron transport material, preferably asmatrix material and/or hole/exciton blocker material, in OLEDs are thus,for example, also carbene complexes as described in WO 2005/019373 A2,WO 2006/056418 A2, WO 2005/113704, WO 2007/115970, WO 2007/115981 and WO2008/000727. Explicit reference is made here to the disclosure of the WOapplications cited, and these disclosures shall be considered to beincorporated into the content of the present application.

Preferably, the light-emitting layer (e) comprises at least one emittermaterial and at least one host material. Suitable and preferred emittermaterials as well as suitable and preferred host materials are mentionedabove.

The individual layers among the aforementioned layers of the OLED may inturn be formed from two or more layers. For example, the hole-transportlayer may be formed from one layer, into which holes are injected fromthe electrode, and a layer which transports the holes away from thehole-injecting layer into the light-emitting layer. Theelectron-transport layer may likewise consist of a plurality of layers,for example of a layer in which electrons are injected through theelectrode and a layer which receives electrons from theelectron-injecting layer and transports them into the light-emittinglayer. These layers mentioned are each selected according to factorssuch as energy level, thermal resistance and charge carrier mobility,and also energy difference of the layers mentioned with the organiclayers or the metal electrodes. The person skilled in the art is capableof selecting the construction of the OLEDs such that it is matchedoptimally to the inventive metal-carbene complexes used as emittersubstances in accordance with the invention.

In order to obtain particularly efficient OLEDs, the HOMO (highestoccupied molecular orbital) of the hole-transport layer should bealigned to the work function of the anode, and the LUMO (lowestunoccupied molecular orbital) of the electron-transport layer should bealigned to the work function of the cathode.

The present application further provides an OLED comprising at least oneinventive light-emitting layer. The further layers in the OLED may beformed from any material which is typically used in such layers and isknown to those skilled in the art.

Suitable materials for the aforementioned layers (anode, cathode, holeand electron injection materials, hole and electron transport materialsand hole and electron blocker materials, matrix materials, fluorescenceand phosphorescence emitters) are known to those skilled in the art andare specified, for example, in H. Meng, N. Herron, Organic SmallMolecule Materials for Organic Light-Emitting Devices in OrganicLight-Emitting Materials and Devices, eds: Z. Li, H. Meng, Taylor &Francis, 2007, Chapter 3, pages 295 to 411.

Anode (a)

The anode is an electrode which provides positive charge carriers. Itmay be composed, for example, of materials which comprise a metal, amixture of different metals, a metal alloy, a metal oxide or a mixtureof different metal oxides. Alternatively, the anode may be a conductivepolymer. Suitable metals comprise the metals of groups 11, 4, 5 and 6 ofthe Periodic Table of the Elements, and also the transition metals ofgroups 8 to 10. When the anode is to be transparent, mixed metal oxidesof groups 12, 13 and 14 of the Periodic Table of the Elements aregenerally used, for example indium tin oxide (ITO). It is likewisepossible that the anode (1) comprises an organic material, for examplepolyaniline, as described, for example, in Nature, Vol. 357, pages 477to 479 (Jun. 11, 1992). Preferred anode materials include conductivemetal oxides, such as indium tin oxide (ITO) and indium zinc oxide(IZO), aluminum zinc oxide (AlZnO), and metals. Anode (and substrate)may be sufficiently transparent to create a bottom-emitting device. Apreferred transparent substrate and anode combination is commerciallyavailable ITO (anode) deposited on glass or plastic (substrate). Areflective anode may be preferred for some top-emitting devices, toincrease the amount of light emitted from the top of the device. Atleast either the anode or the cathode should be at least partlytransparent in order to be able to emit the light formed. Other anodematerials and structures may be used.

The anode materials mentioned above are commercially available and/orprepared by processes known by a person skilled in the art.

Hole Transport Layer (c)

Suitable hole transport materials for layer (c) of the inventive OLEDare disclosed, for example, in Kirk-Othmer Encyclopedia of ChemicalTechnology, 4th Edition, Vol. 18, pages 837 to 860, 1996. Eitherhole-transporting molecules or polymers may be used as thehole-transport material. Customarily used hole-transporting moleculesare selected from the group consisting of

(4-phenyl-N-(4-phenylphenyl)-N-[4-[4-(N-[4-(4-phenylphenyl)phenyl]anilino)phenyl]phenyl]aniline),

(4-phenyl-N-(4-phenylphenyl)-N-[4-[4-(4-phenyl-N-(4-phenylphenyl)anilino)phenyl]phenyl]aniline),

(4-phenyl-N-[4-(9-phenylcarbazol-3-yl)phenyl]-N-(4-phenylphenyl)aniline),

1,1′,3,3′-tetraphenylspiro[1,3,2-benzodiazasilole-2,2′-3a,7a-dihydro-1,3,2-benzodiazasilole],

(N2,N2,N2′,N2′,N7,N7,N7′,N7′-octa-kis(p-tolyl)-9,9′-spirobi[fluorene]-2,2′,7,7′-tetramine),4,4′-bis[N-(1-naphthyl)-N-phenyl-amino]biphenyl (α-NPD),N,N′-diphenyl-N, N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine(TPD), 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), N,N′-bis(4-methylphenyl)-N, N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]-4,4′-diamine (ETPD),tetrakis(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine (PDA),α-phenyl-4-N,N-diphenylaminostyrene (TPS), p-(diethylamino)benzaldehydediphenyl-hydrazone (DEH), triphenylamine (TPA),bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane (MPMP),1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyrazoline(PPR or DEASP), 1,2-trans-bis(9H-carbazol-9-yl)-cyclobutane (DCZB),N,N,N′,N′-tetrakis(4-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine (TTB),fluorine compounds such as2,2′,7,7′-tetra(N,N-di-tolyl)amino9,9-spirobifluorene (spiro-TTB),N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)_(9,9)-spirobifluorene(spiro-NPB) and9,9-bis(4-(N,N-bis-biphenyl-4-yl-amino)phenyl-9Hfluorene, benzidinecompounds such as N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)benzidineand porphyrin compounds such as copper phthalocyanines. In addition,polymeric hole-injection materials can be used such aspoly(N-vinylcarbazole) (PVK), polythiophenes, polypyrrole, polyaniline,self-doping polymers, such as, for example, sulfonatedpoly(thiophene-3-[2[(2-methoxyethoxy)-ethoxy]-2,5-diyl) (Plexcore® OCConducting Inks commercially available from Plextronics), and copolymerssuch as poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) alsocalled PEDOT/PSS.

In addition—in one embodiment—it is possible to use metal carbenecomplexes as hole conductor materials, in which case the band gap of theat least one hole conductor material is generally greater than the bandgap of the emitter material used. In the context of the presentapplication, band gap is understood to mean the triplet energy. Suitablecarbene complexes are, for example, metal carbene complexes as describedin WO2005/019373A2, WO2006/056418 A2, WO2005/113704, WO2007/115970,WO2007/115981 and WO2008/000727. One example of a suitable carbenecomplex is Ir(DPBIC)₃ with the formula:

Another example of a suitable carbene complex is Ir(DPABIC)₃

The preparation of Ir(DPABIC)₃ is for example mentioned in WO2012/172182(as complex fac-Em1; synthesis: example 1)).

The hole-transport layer may also be electronically doped in order toimprove the transport properties of the materials used, in order firstlyto make the layer thicknesses more generous (avoidance of pinholes/shortcircuits) and in order secondly to minimize the operating voltage of thedevice. Electronic doping is known to those skilled in the art and isdisclosed, for example, in W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, No.1, 1 Jul. 2003 (p-doped organic layers); A. G. Werner, F. Li, K. Harada,M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., Vol. 82, No. 25, 23Jun. 2003 and Pfeiffer et al., Organic Electronics 2003, 4, 89-103 andK. Walzer, B. Maennig, M. Pfeiffer, K. Leo, Chem. Soc. Rev. 2007, 107,1233. For example it is possible to use mixtures in the hole-transportlayer, in particular mixtures which lead to electrical p-doping of thehole-transport layer. p-Doping is achieved by the addition of oxidizingmaterials. These mixtures may, for example, be the following mixtures:mixtures of the abovementioned hole transport materials with at leastone metal oxide, for example MoO₂, MoO₃, WOx, ReO₃ and/or V₂O₅,preferably MoO₃ and/or ReO₃, more preferably ReO₃ or mixtures comprisingthe aforementioned hole transport materials and one or more compoundsselected from 7,7,8,8-tetracyanoquinodimethane (TCNQ),2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F₄-TCNQ),2,5-bis(2-hydroxyethoxy)-7,7,8,8-tetracyanoquinodimethane,bis(tetra-n-butylammonium)tetracyanodiphenoquinodimethane,2,5-dimethyl-7,7,8,8-tetracyanoquinodimethane, tetracyanoethylene,11,11,12,12-tetracyanonaphtho-2,6-quinodimethane,2-fluoro-7,7,8,8-tetracyanoquino-dimethane,2,5-difluoro-7,7,8,8-etracyanoquinodimethane,dicyanomethylene-1,3,4,5,7,8-hexafluoro-6H-naphthalen-2-ylidene)malononitrile(F₆-TNAP), Mo(tfd)₃ (from Kahn et al., J. Am. Chem. Soc. 2009, 131 (35),12530-12531), compounds as described in EP1988587 and in EP2180029 andquinone compounds as mentioned in EP2401254.

Electron-Transport Layer (g)

Electron transport layer may include a material capable of transportingelectrons. Electron transport layer may be intrinsic (undoped), ordoped. Doping may be used to enhance conductivity. Suitableelectron-transport materials for layer (g) of the inventive OLEDscomprise metals chelated with oxinoid compounds, such astris(8-hydroxyquinolato)aluminum (Alq₃), compounds based onphenanthroline such as 2,9-dimethyl-4,7-diphenyl-1,10phenanthroline(DDPA=BCP), 4,7-diphenyl-1,10-phenanthroline (Bphen),2,4,7,9-tetraphenyl-1,10-phenanthroline,4,7-diphenyl-1,10-phenanthroline (DPA) or phenanthroline derivativesdisclosed in EP1786050, in EP1970371, or in EP1097981, and azolecompounds such as 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole(PBD) and 3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole(TAZ). Layer (g) may serve both to ease the electron transport and as abuffer layer or as a barrier layer in order to prevent quenching of theexciton at the interfaces of the layers of the OLED. Layer (g)preferably improves the mobility of the electrons and reduces quenchingof the exciton. The electron-transport materials mentioned above arecommercially available and/or prepared by processes known by a personskilled in the art.

It is likewise possible to use mixtures of at least two materials in theelectron-transport layer, in which case at least one material iselectron-conducting. Preferably, in such mixed electron-transportlayers, at least one phenanthroline compound is used, preferably BCP (incombination with Cs₂CO₃), or at least one pyridine compound according tothe formula (VIII) below, preferably a compound of the formula (VIIlaa)below. More preferably, in mixed electron-transport layers, in additionto at least one phenanthroline compound, alkaline earth metal or alkalimetal hydroxyquinolate complexes, for example Liq, are used. Suitablealkaline earth metal or alkali metal hydroxyquinolate complexes arespecified below (formula VII). Reference is made to WO2011/157779.

The electron-transport layer may also be electronically doped in orderto improve the transport properties of the materials used, in orderfirstly to make the layer thicknesses more generous (avoidance ofpinholes/short circuits) and in order secondly to minimize the operatingvoltage of the device. Electronic doping is known to those skilled inthe art and is disclosed, for example, in W. Gao, A. Kahn, J. Appl.Phys., Vol. 94, No. 1, 1 Jul. 2003 (p-doped organic layers); A. G.Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys.Lett., Vol. 82, No. 25, 23 Jun. 2003 and Pfeiffer et al., OrganicElectronics 2003, 4, 89-103 and K. Walzer, B. Maennig, M. Pfeiffer, K.Leo, Chem. Soc. Rev. 2007, 107, 1233.

For example, it is possible to use mixtures which lead to electricaln-doping of the electron-transport layer. n-Doping is achieved by theaddition of reducing materials. These mixtures may, for example, bemixtures of the abovementioned electron transport materials withalkali/alkaline earth metals or alkali/alkaline earth metal salts, forexample Li, Cs, Ca, Sr, Cs₂CO₃, with alkali metal complexes, for example8-hydroxyquinolatolithium (Liq), and with Y, Ce, Sm, Gd, Tb, Er, Tm, Yb,Li₃N, Rb₂CO₃, dipotassium phthalate, W(hpp)₄ from EP 1786050, or withcompounds as described in EP1837926B1.

In a preferred embodiment, the electron-transport layer comprises atleast one compound of the general formula (VII)

in whichR³² and R³³ are each independently F, C₁-C₈-alkyl, or C₆-C₁₄-aryl, whichis optionally substituted by one or more C₁-C₈-alkyl groups, or two R³²and/or R³³ substituents together form a fused benzene ring which isoptionally substituted by one or more C₁-C₈-alkyl groups;a and b are each independently 0, or 1, 2 or 3,M¹ is an alkaline metal atom or alkaline earth metal atom,p is 1 when M¹ is an alkali metal atom, p is 2 when M¹ is an alkalimetal atom.

A very particularly preferred compound of the formula (VII) is

which may be present as a single species, or in other forms such asLi_(g)Q_(g) in which g is an integer, for example Li₆Q₆. Q is an8-hydroxyquinolate ligand or an 8-hydroxyquinolate derivative.

In a further preferred embodiment, the electron-transport layercomprises at least one compound of the formula (VIII),

in whichR³⁴, R³⁵, R³⁶, R³⁷, R^(34′), R^(35′), R^(36′) and R^(37′) are eachindependently H, C₁-C₁₈-alkyl, C₁-C₁₈-alkyl which is substituted by Eand/or interrupted by D, C₆-C₂₄-aryl, C₆-C₂₄-aryl which is substitutedby G, C₂-C₂₀-heteroaryl or C₂-C₂₀-heteroaryl which is substituted by G,Q is an arylene or heteroarylene group, each of which is optionallysubstituted by G;D is —CO—; —COO—; —S—; —SO—; —SO₂—; —O—; —NR⁴⁰—; —SiR⁴⁵R⁴⁶—; —POR⁴⁷—;—CR³⁸═CR³⁹—; or —C≡C—;E is —OR⁴⁴; —SR⁴⁴; —NR⁴⁰R⁴¹; —COR⁴³; —COOR⁴²; —CONR⁴⁰R⁴¹; —CN; or F;G is E, C₁-C₁₈-alkyl, C₁-C₁₈-alkyl which is interrupted by D,C₁-C₁₈-perfluoroalkyl, C₁-C₁₈-alkoxy, or C₁-C₁₈-alkoxy which issubstituted by E and/or interrupted by D, in whichR³⁸ and R³⁹ are each independently H, C₆-C₁₈-aryl; C₆-C₁₈-aryl which issubstituted by C₁-C₁₈-alkyl or C₁-C₁₈-alkoxy; C₁-C₁₈-alkyl; orC₁-C₁₈-alkyl which is interrupted by —O—;R⁴⁰ and R⁴¹ are each independently C₆-C₁₈-aryl; C₆-C₁₈-aryl which issubstituted by C₁-C₁₈-alkyl or C₁-C₁₈-alkoxy; C₁-C₁₈-alkyl; orC₁-C₁₈-alkyl which is interrupted by —O—; orR⁴⁰ and R⁴¹ together form a 6-membered ring;R⁴² and R⁴³ are each independently C₆-C₁₈-aryl; C₆-C₁₈-aryl which issubstituted by C₁-C₁₈-alkyl or C₁-C₁₈-alkoxy; C₁-C₁₈-alkyl; orC₁-C₁₈-alkyl which is interrupted by —O—,R⁴⁴ is C₆-C₁₈-aryl; C₆-C₁₈-aryl which is substituted by C₁-C₁₈-alkyl orC₁-C₁₈-alkoxy; C₁-C₁₈-alkyl; or C₁-C₁₈-alkyl which is interrupted by—O—,R⁴⁵ and R⁴⁶ are each independently C₁-C₁₈-alkyl, C₆-C₁₈-aryl orC₆-C₁₈-aryl which is substituted by C₁-C₁₈-alkyl,R⁴⁷ is C₁-C₁₈-alkyl, C₆-C₁₈-aryl or C₆-C₁₈-aryl which is substituted byC₁-C₁₈-alkyl.

Preferred compounds of the formula (VIII) are compounds of the formula(Villa)

in which Q is:

R⁴⁸ is H or C₁-C₁₈-alkyl andR^(48′) is H, C₁-C₁₈-alkyl or

Particular preference is given to a compound of the formula (VIIIaa)

In a further, very particularly preferred embodiment, theelectron-transport layer comprises a compound of the formula

and a compound of the formula

In a preferred embodiment, the electron-transport layer comprises thecompound of the formula (VII) in an amount of 99 to 1% by weight,preferably 75 to 25% by weight, more preferably about 50% by weight,where the amount of the compounds of the formulae (VII) and the amountof the compounds of the formulae (VIII) adds up to a total of 100% byweight.

The preparation of the compounds of the formula (VIII) is described inJ. Kido et al., Chem. Commun. (2008) 5821-5823, J. Kido et al., Chem.Mater. 20 (2008) 5951-5953 and JP2008-127326, or the compounds can beprepared analogously to the processes disclosed in the aforementioneddocuments.

It is likewise possible to use mixtures of alkali metal hydroxyquinolatecomplexes, preferably Liq, and dibenzofuran compounds in theelectron-transport layer. Reference is made to WO2011/157790.Dibenzofuran compounds A-1 to A-36 and B-1 to B-22 described inWO2011/157790 are preferred, wherein dibenzofuran compound

(A-10; =ETM-2) is most preferred.

In a preferred embodiment, the electron-transport layer comprises Liq inan amount of 99 to 1% by weight, preferably 75 to 25% by weight, morepreferably about 50% by weight, where the amount of Liq and the amountof the dibenzofuran compound(s), especially compound A-10, adds up to atotal of 100% by weight.

In a preferred embodiment, the invention relates to an inventive OLEDwherein the electron-transport layer comprises at least onephenanthroline derivative and/or pyridine derivative.

In a further preferred embodiment, the invention relates to an inventiveOLED wherein the electron-transport layer comprises at least onephenanthroline derivative and/or pyridine derivative and at least onealkali metal hydroxyquinolate complex.

In a further preferred embodiment, the invention relates to an inventiveOLED wherein the electron-transport layer comprises at least onephenanthroline derivative and/or pyridine derivative and8-hydroxyquinolatolithium.

In a further preferred embodiment, the electron transport layercomprises at least one of the dibenzofuran compounds A-1 to A-36 and B-1to B-22 described in WO2011/157790, especially A-10.

In a further preferred embodiment, the electron transport layercomprises a compound described in WO 2012/111462, WO 2012/147397 and US2012/0261654, such as, for example, a compound of formula

WO 2012/115034, such as for example, such as, for example, a compound offormula

Some of the materials mentioned above as hole transport materials andelectron-transport materials can fulfill several functions. For example,some of the electron-transport materials are simultaneouslyhole-blocking materials if they have a low-lying HOMO.

Cathode (i)

The cathode (i) is an electrode which serves to introduce electrons ornegative charge carriers. The cathode may be any metal or nonmetal whichhas a lower work function than the anode. Suitable materials for thecathode are selected from the group consisting of alkali metals of group1, for example Li, Cs, alkaline earth metals of group 2, metals of group12 of the Periodic Table of the Elements, comprising the rare earthmetals and the lanthanides and actinides. In addition, metals such asaluminum, indium, calcium, barium, samarium and magnesium, andcombinations thereof, may be used. The cathode materials mentioned aboveare commercially available and/or prepared by processes known by aperson skilled in the art.

Hole injection layer (b) Generally, injection layers are comprised of amaterial that may improve the injection of charge carriers from onelayer, such as an electrode or a charge generating layer, into anadjacent organic layer. Injection layers may also perform a chargetransport function. The hole injection layer (b) may be any layer thatimproves the injection of holes from anode into an adjacent organiclayer. A hole injection layer may comprise a solution depositedmaterial, such as a spin-coated polymer, or it may be a vapor depositedsmall molecule material, such as, for example, CuPc or MTDATA. Polymerichole-injection materials can be used such as poly(N-vinylcarbazole)(PVK), polythiophenes, polypyrrole, polyaniline, self-doping polymers,such as, for example, sulfonatedpoly(thiophene-3-[2[(2-methoxyethoxy)ethoxy]-2,5-diyl) (Plexcore® OCConducting Inks commercially available from Plextronics), and copolymerssuch as poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) alsocalled PEDOT/PSS.

The hole injection materials mentioned above are commercially availableand/or prepared by processes known by a person skilled in the art.

Electron Injection Layer (h)

The electron injection layer (h) may be any layer that improves theinjection of electrons into an adjacent organic layer.Lithium-comprising organometallic compounds such as8-hydroxyquinolatolithium (Liq), CsF, NaF, KF, Cs₂CO₃ or LiF may beapplied between the electron transport layer (g) and the cathode (i) asan electron injection layer in order to reduce the operating voltage.

The electron injection materials mentioned above are commerciallyavailable and/or prepared by processes known by a person skilled in theart.

Those skilled in the art know how suitable materials have to be selected(for example on the basis of electrochemical investigations). Suitablematerials for the individual layers are known to those skilled in theart and disclosed, for example, in WO00/70655.

In addition, it is possible that some or all of the layers (b) to (h)have been surface-treated in order to increase the efficiency of chargecarrier transport. The selection of the materials for each of the layersmentioned is preferably determined by obtaining an OLED having a highefficiency.

The inventive OLED can be produced by methods known to those skilled inthe art. In general, the OLED is produced by successive vapor depositionof the individual layers onto a suitable substrate. Suitable substratesare, for example, glass, inorganic materials such as ITO or IZO orpolymer films. For the vapor deposition, customary techniques may beused, such as thermal evaporation, chemical vapor deposition (CVD),physical vapor deposition (PVD) and others.

In an alternative process, the organic layers may be coated fromsolutions or dispersions in suitable solvents, in which case coatingtechniques known to those skilled in the art are employed. Suitablecoating techniques are, for example, spin-coating, the casting method,the Langmuir-Blodgett (“LB”) method, the inkjet printing method,dip-coating, letterpress printing, screen printing, doctor bladeprinting, slit-coating, roller printing, reverse roller printing, offsetlithography printing, flexographic printing, web printing, spraycoating, coating by a brush or pad printing, and the like. Among theprocesses mentioned, in addition to the aforementioned vapor deposition,preference is given to spin-coating, the inkjet printing method and thecasting method since they are particularly simple and inexpensive toperform. In the case that layers of the OLED are obtained by thespin-coating method, the casting method or the inkjet printing method,the coating can be obtained using a solution prepared by dissolving thecomposition in a concentration of 0.0001 to 90% by weight in a suitableorganic solvent such as benzene, toluene, xylene, tetrahydrofuran,methyltetrahydrofuran, N,N-dimethylformamide, acetone, acetonitrile,anisole, dichloromethane, dimethyl sulfoxide, water and mixturesthereof.

It is possible that the layers of the OLED are all produced by the samecoating method. Furthermore, it is likewise possible to conduct two ormore different coating methods to produce the layers of the OLED.

In general, the different layers in the inventive OLED, if present, havethe following thicknesses:

anode (a): 50 to 500 nm, preferably 100 to 200 nm;hole injection layer (b): 5 to 100 nm, preferably 20 to 80 nm,hole-transport layer (c): 5 to 100 nm, preferably 10 to 80 nm;electron/exciton blocking layer (d): 1 to 50 nm, preferably 5 to 10 nm,light-emitting layer (e): 1 to 100 nm, preferably 5 to 60 nm;hole/exciton blocking layer (f): 1 to 50 nm, preferably 5 to 10 nm,electron-transport layer (g): 5 to 100 nm, preferably 20 to 80 nm;electron injection layer (h): 1 to 50 nm, preferably 2 to 10 nm;cathode (i): 20 to 1000 nm, preferably 30 to 500 nm.

In addition to the compounds of the formula (X), according to thepresent invention, it is also possible to use crosslinked or polymericmaterials comprising repeat units based on the general formula (X) incrosslinked or polymerized form together with at least one inventivemetal-carbene complex. Like the compounds of the general formula (X),the latter are preferably used as matrix materials.

The crosslinked or polymeric materials have outstanding solubility inorganic solvents, excellent film-forming properties and relatively highglass transition temperatures. In addition, high charge carriermobilities, high stabilities of color emission and long operating timesof the corresponding components can be observed when crosslinked orpolymeric materials according to the present invention are used inorganic light-emitting diodes (OLEDs).

The crosslinked or polymerized materials are particularly suitable ascoatings or in thin films since they are thermally and mechanicallystable and relatively defect-free.

The crosslinked or polymerized materials comprising repeating unitsbased on the general formula (X) can be prepared by a process comprisingsteps (a) and (b):

-   (a) preparation of a crosslinkable or polymerizable compound of the    general formula (X) where at least one of the ml R²⁰⁴ radicals or at    least one of the n2 R²⁰⁵ radicals is a crosslinkable or    polymerizable group attached via a spacer, and-   (b) crosslinking or polymerization of the compound of the general    formula (X) obtained from step (a).

The crosslinked or polymerized materials may be homopolymers, whichmeans that exclusively units of the general formula (X) are present incrosslinked or polymerized form. They may also be copolymers, whichmeans that further monomers are present in addition to the units of thegeneral formula (X), for example monomers with hole-conducting and/orelectron-conducting properties, in crosslinked or polymerized form.

In a further preferred embodiment of the inventive OLED, it comprises anemission layer comprising at least one inventive metal-carbene complex,at least one matrix material of the formula (X), and optionally at leastone further hole-transport matrix material.

The inventive OLEDs can be used in all devices in whichelectroluminescence is useful. Suitable devices are preferably selectedfrom stationary and mobile visual display units and illumination means.The present invention therefore also relates to a device selected fromthe group consisting of stationary visual display units and mobilevisual display units and illumination means, comprising an inventiveOLED.

Stationary visual display units are, for example, visual display unitsof computers, televisions, visual display units in printers, kitchenappliances and advertising panels, illuminations and information panels.Mobile visual display units are, for example, visual display units incellphones, laptops, tablet PCs, digital cameras, mp-3 players,smartphones, vehicles, and destination displays on buses and trains.

The inventive metal-carbene complexes can additionally be used in OLEDswith inverse structure. In these inverse OLEDs, the inventive complexesare in turn preferably used in the light-emitting layer. The structureof inverse OLEDs and the materials typically used therein are known tothose skilled in the art.

The present invention further provides a white OLED comprising at leastone inventive metal-carbene complex. In a preferred embodiment, theinventive metal-carbene complexes are used as emitter material in thewhite OLED. Preferred embodiments of the inventive metal-carbenecomplexes have been specified above. In addition to the at least oneinventive metal-carbene complex, the white OLED may comprise

-   (i) at least one compound of the formula (X). The compound of the    formula (X) is preferably used as matrix material. Preferred    compounds of the formula (X) have been specified above; and/or-   (ii) at least one compound of the formula (VII) and/or (IX). The    compounds of the formula (VII) and/or (IX) are preferably used as    electron transport material. Preferred compounds of the    formulae (VII) and (IX) have been specified above.

In order to obtain white light, the OLED must generate light whichcolors the entire visible range of the spectrum. However, organicemitters normally emit only in a limited portion of the visiblespectrum—i.e. are colored. White light can be generated by thecombination of different emitters. Typically, red, green and blueemitters are combined. However, the prior art also discloses othermethods for formation of white OLEDs, for example the triplet harvestingapproach. Suitable structures for white OLEDs or methods for formationof white OLEDs are known to those skilled in the art.

In one embodiment of a white OLED, several dyes are layered one on topof another in the light-emitting layer of an OLED and hence combined(layered device). This can be achieved by mixing all dyes or by directseries connection of different-colored layers. The expression “layeredOLED” and suitable embodiments are known to those skilled in the art.

In a further embodiment of a white OLED, several different-colored OLEDsare stacked one on top of another (stacked device). For the stacking oftwo OLEDs, what is called a charge generation layer (CG layer) is used.This CG layer may be formed, for example, from one electrically n-dopedand one electrically p-doped transport layer. The expression “stackedOLED” and suitable embodiments are known to those skilled in the art.

In further embodiments of this “stacked device concept”, it is alsopossible to stack only two OLEDs or to stack more than three OLEDs.

In a further embodiment of white OLEDs, the two concepts mentioned forwhite light generation can also be combined. For example, a single-colorOLED (for example blue) can be stacked with a multicolor layered OLED(for example red-green). Further combinations of the two concepts areconceivable and known to those skilled in the art.

The inventive metal-carbene complexes can be used in any of the layersmentioned above in white OLEDs. In a preferred embodiment, it is used inone or more or all light-emitting layer(s) of the OLED(s), in which casethe structure of the invention metal-carbene complex is varied as afunction of the use of the complex. Suitable and preferred componentsfor the further layers of the light OLED(s) or materials suitable asmatrix material in the light-emitting layer(s) and preferred matrixmaterials are likewise specified above.

The present invention also relates to an organic electronic device,preferably an organic light-emitting diode (OLED), organic photovoltaiccell (OPV), organic field-effect transistor (OFET) or light-emittingelectrochemical cell (LEEC), comprising at least one inventivemetal-carbene complex.

The examples which follow, more particularly the methods, materials,conditions, process parameters, apparatus and the like detailed in theexamples, are intended to support the present invention, but not torestrict the scope of the present invention.

EXAMPLES

A variety of representations are used to depict the bonding inmetal-carbenes, including those in which a curved line is used toindicate partial multiple bonding between the carbene carbon and theadjacent heteroatom(s):

In the figures and structures herein, a metal-carbene bond is depictedas C-M, as, for example,

All experiments are carried out in protective gas atmosphere. Thepercentages and ratios mentioned in the examples below—unless statedotherwise—are % by weight and weight ratios.

I. SYNTHESIS EXAMPLES Synthesis Example 1. Synthesis of Complex (A-1) a)Synthesis of 1,3-dimethyl-2-(3-nitrophenyl)benzene

40.8 g (0.20 mol) of 1-bromo-3-nitrobenzene together with 34.0 g (0.22mol) of 2,6-dimethylphenylboronic acid, 230 g (1.00 mol) of potassiumphosphate tribasic monohydrate, 1.23 g (3.0 mmol)) of2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl, and 0.22 g (1.0 mmol)of palladium(II) acetate are suspended in 300 ml of toluene at roomtemperature under argon. The suspension is three times evacuated andbackfilled with argon, followed by heating under reflux for three hours.The beige suspension is filtered through a layer of Hyflo® filter aidand the filter aid rinsed with 200 ml of toluene. The filtrate is threetimes washed with 200 ml of water, the combined organic phases driedover sodium sulfate, concentrated under vacuum, and further purified bychromatography (silica gel, heptane), giving the title product as alight yellow oil (yield: 36.5 g (80%)).

¹H-NMR (400 MHz, CDCl₃): • δ=2.06 (s, 6H), 7.17 (d, 2H), 7.22-7.30 (m,1H), 7.51-7.58 (m, 1H), 7.62-7.69 (m, 1H), 8.07-8.12 (m, 1H), 8.23-8.29(m, 1H).

b) Synthesis of 3-(2,6-dimethylphenyl)aniline

30.0 g (0.132 mol) of 1,3-dimethyl-2-(3-nitrophenyl)benzene and 3.0 g of5 wt %-palladium on carbon are reacted under 3 bar hydrogen pressure at35° C. during 21 hours. The reaction mixture is filtered through a layerof Hyflo® filter aid and rinsed with additional ethanol, followed byconcentration under vacuum. The yellow oil is further purified bychromatography (silica gel, heptane/ethyl acetate 9:1) giving the titleproduct as a light yellow solid (yield: 19.3 g (74%)).

¹H-NMR (400 MHz, CD₂Cl₂): δ=2.09 (s, 6H), 2.86-4.20 (br. s, 2H),6.47-6.57 (m, 2H), 6.67-6.73 (m, 1H), 7.08-7.20 (m, 3H), 7.21-7.27 (m,1H).

c) Synthesis of 3-chloro-N-phenyl-pyrazin-2-amine

59.6 g (0.40 mol) of 2,3-dichloropyrazine, 37.3 g (0.40 mol) of aniline,and 42.4 g (0.40 mol) of sodium carbonate are suspended in 250 ml of1-methyl-pyrrolidone and heated at 151° C. during 24 hours. The blacksuspension is cooled down to 100° C., filtered, and the solid residuefurther washed with ethyl acetate. The filtrate is concentrated undervacuum and the residual oil further purified by distillation (125-128°C., 0.3 mbar) giving the title product as light yellow solid (yield:58.3 g (71%)).

¹H-NMR (300 MHz, CDCl₃): δ=7.05-7.22 (m, 2H), 7.32-7.45 (m, 2H),7.57-7.68 (m, 2H), 7.75 (d, 1H), 8.05 (d, H).

d) Synthesis ofN3-[3-(2,6-dimethylphenyl)phenyl]-N2-phenyl-pyrazine-2,3-diamine

9.38 g (45.6 mmol) of 3-chloro-N-phenyl-pyrazin-2-amine, and 9.00 g(45.6 mmol) of 3-(2,6-dimethylphenyl)aniline, and 0.21 g (0.23 mmol) oftris(dibenzylideneacetone)dipalladium(0), and 0.43 g (0.69 mmol) of2,2′-bis(diphenylphosphino)-1,1′-binaphthalene, and 6.14 g (63.9 mmol)of sodium tert-butoxide are suspended in 100 ml of toluene at roomtemperature under argon. The red-brown suspension is three timesevacuated and backfilled with argon, followed by heating under refluxfor 49 hours. An additional 0.21 g (0.23 mmol) oftris(dibenzylideneacetone)dipalladium(0), and 0.43 g (0.69 mmol)2,2′-bis(diphenylphosphino)-1,1′-binaphthalene are added and heatingcontinued for 23 hours. An additional 0.11 g (0.12 mmol) oftris(dibenzylideneacetone)dipalladium(0), and 0.22 g (0.35 mmol)2,2′-bis(diphenylphosphino)-1,1′-binaphthalene are added and heatingcontinued for 6 hours giving a beige suspension. The reaction mixture iscooled down to room temperature and 200 ml of hexane are added followedby filtration. The solid residue is further washed with hexane and takenup in 200 ml of water followed by filtration and washing with plenty ofwater. The solid is taken up in 300 ml of 5%-ammonia solution, stirredduring 30 minutes, followed by filtration and washing with 200 ml ofwater. The brown solid is dissolved in 300 ml ethyl acetate and filteredthrough a 4 cm layer of silica gel followed by rinsing the silica gellayer with ethyl acetate. The combined ethyl acetate fractions areconcentrated under vacuum and the resulting brown viscous oil dissolvedin dichloromethane followed by filtration through a 4 cm layer of silicagel and additional rinsing of the silica gel layer with dichloromethane.The combined eluents are concentrated under vacuum giving the titleproduct as beige solid (yield: 8.9 g (53%)).

¹H-NMR (400 MHz, d₆-DMSO): δ=2.05 (s, 6H), 6.73-6.78 (m, 1H), 6.96-7.02(m, 1H), 7.09-7.20 (m, 3H), 7.29-7.35 (m, 2H), 7.41 (t, 1H), 7.45-7.48(m, 1H), 7.56-7.60 (m, 2H), 7.63-7.72 (m, 3H), 8.53 (br. s, 1H), 8.58(br. s, 1H).

e) Synthesis of(3-anilinopyrazin-2-yl)-[3-(2,6-dimethylphenyl)phenyl]ammonium chloride

A beige suspension of 5.0 g (13.6 mmol) ofN3-[3-(2,6-dimethylphenyl)phenyl]-N2-phenyl-pyrazine-2,3-diamine and 100ml of 37% hydrochloric acid is stirred at room temperature during 21hours. The suspension is filtered and further washed with 37%hydrochloric acid and plenty of hexane, followed by drying in a vacuumoven, giving the title product as a beige solid (yield: 5.4 g (99%)).

¹H-NMR (400 MHz, d₆-DMSO): δ=2.04 (s, 6H), 6.87 (d, 1H), 7.09-7.20 (m,4H), 7.37-7.49 (m, 4H), 7.52 (d, 1H), 7.61-7.65 (m, 1H), 7.73 (d, 2H),7.84-7.90 (m, 1H), 10.37 (br. s, 1H), 10.59 (br. s, 1H).

f) Synthesis of3-[3-(2,6-dimethylphenyl)phenyl]-2-ethoxy-1-phenyl-2H-imidazo[4,5-b]-pyrazine

5.0 g (12.4 mmol) of(3-anilinopyrazin-2-yl)-[3-(2,6-dimethylphenyl)phenyl]ammonium chlorideand 90 g (0.61 mol) of triethyl orthoformate are heated up under argonat 100° C. during one hour. The light brown solution is filtered througha layer of Hyflo® filter aid and the filter aid rinsed with 10 ml oftriethyl orthoformate. The filtrate is concentrated under vacuum givingthe title product as off-white solid (yield: 5.1 g (97%)).

¹H-NMR (400 MHz, d₆-DMSO): δ=0.89 (t, 3H), 2.04 (s, 6H), 3.20 (q, 2H),6.96 (d, 1H), 7.12-7.23 (m, 4H), 7.42-7.49 (m, 2H), 7.50-7.60 (m, 3H),7.76-7.79 (m, 1H), 7.87 (s, 1H), 8.03-8.08 (m, 2H), 8.18-8.24 (m, 1H).

g) Synthesis of Complex (A-1)

3.2 g (7.6 mmol) of3-[3-(2,6-dimethylphenyl)phenyl]-2-ethoxy-1-phenyl-2H-imidazo[4,5-b]-pyrazineand 0.62 g (0.92 mmol) of chloro(1,5-cyclooctadiene)iridium(I) dimer aresuspended under argon in 30 ml of o-xylene. The suspension is four timesevacuated and backfilled with argon, followed by heating at 135° C.during 19 hours. The dark brown solution is cooled down to roomtemperature, diluted with 50 ml of dichloromethane and filtered througha 3 cm layer of silica gel followed by rinsing the silica gel layer with200 ml of dichloromethane. The filtrate is concentrated and furthersuspended in 75 ml of hot ethanol providing precipitation of some solid.The filtrate is several times re-concentrated and treated by ethanol andhexane to provide further precipitation, giving a fraction of 0.51 gproduct mixture. The yellow powder is further purified by chromatography(silica gel, hexane/ethyl acetate) giving the title product as yellowsolid (yield: 89.7 mg (4%)). APCI-LC-MS (positive, m/z): exact mass ofC₇₅H₅₇IrN₁₂=1318.44; found 1319.6 [M+1]⁺.

Synthesis Example 2. Synthesis of Complex (A-15) a) Synthesis of3-chloro-N-(3,5-dimethylphenyl)pyrazin-2-amine

74.5 g (0.50 mol) of 2,3-dichloropyrazine, 60.6 g (0.50 mol) of3,5-dimethylaniline and 53.0 g (0.50 mol) of sodium carbonate aresuspended in 250 ml of 1-methyl-pyrrolidone and heated at 151° C. during48 hours. The brown suspension is cooled down to room temperature,poured into 2 l of water, stirred during 30 minutes and filtered. Thesolid residue is washed with 2 l of water and dried under vacuum at 50°C. The solid is dissolved in 600 ml of ethyl acetate and filteredthrough a 7 cm layer of silica gel followed by rinsing the silica gelwith plenty of ethyl acetate. The filtrate is concentrated under vacuumand dissolved in 500 ml of hot ethanol giving a brown solution. Thesolution is cooled down to ice-bath temperature and stirred at the sametemperature during one hour. The resulting precipitate is further washedwith ethanol and dried under vacuum at 50° C., giving the title productas a beige solid (yield: 47.9 g (41%)).

¹H-NMR (400 MHz, d₆-DMSO): δ=2.26 (s, 6H), 6.73 (s, 1H), 7.29 (s, 2H),7.79 (d, 1H), 8.13 (d, 1H), 8.59 (s, 1H).

b) Synthesis ofN3-(3,5-dimethylphenyl)-N2-[3-(2,6-dimethylphenyl)phenyl]-pyrazine-2,3-diamine

11.9 g (50.7 mmol) of 3-chloro-N-(3,5-dimethylphenyl)pyrazin-2-amine,and 10.0 g (50.7 mmol) of 3-(2,6-dimethylphenyl)aniline, and 0.23 g(0.25 mmol) of tris(dibenzylidene-acetone)dipalladium(0), and 0.47 g(0.75 mmol) 2,2′-bis(diphenylphosphino)-1,1′-binaphthalene, and 6.82 g(71.0 mmol) of sodium tert-butoxide are suspended in 125 ml of tolueneat room temperature under argon. The brown suspension is three timesevacuated and backfilled with argon, followed by heating under refluxfor seven hours. The reaction mixture is cooled down to room temperatureand filtered through a layer of Hyflo® filter aid and the filter aidrinsed with toluene. The filtrate is diluted with heptane (volume ratio1:1) giving a precipitate which is filtered and washed with heptane,followed by three times washing with water. The solid is dried undervacuum at 50° C. and further dissolved in 500 ml of hot ethanol. Theturbid solution is filtered through a 3 cm layer of Hyflo® filter aidand the filter aid rinsed with 30 ml of hot ethanol. The filtrate iscooled down to room temperature giving a beige suspension which isfurther stirred at ice-bath temperature for one hour. The suspension isfiltered, the solid washed with 100 ml of cold ethanol and further driedunder vacuum, giving the title product as a beige solid (yield: 9.6 g(48%)).

¹H-NMR (400 MHz, d₆-DMSO): δ=2.04 (s, 6H), 2.26 (s, 6H), 6.64 (s, 1H),6.73-6.78 (m, 1H), 7.10-7.20 (m, 3H), 7.29 (s, 2H), 7.40 (t, 1H),7.44-7.48 (m, 1H), 7.56 (d, 1H), 7.59 (d, 1H), 7.66-7.72 (m, 1H), 8.39(br. s, 1H), 8.57 (br. s, 1H).

c) Synthesis of[3-(3,5-dimethylanilino)pyrazin-2-yl]-[3-(2,6-dimethylphenyl)phenyl]-ammoniumchloride

A suspension of 9.0 g (22.8 mmol)N3-(3,5-dimethylphenyl)-N2-[3-(2,6-dimethylphenyl)-phenyl]pyrazine-2,3-diamineand 180 ml of 37% hydrochloric acid is stirred at room temperatureduring 20 hours. The resulting dark viscous oil is separated from theliquid phase by decantation and directly used for the next step.

d) Synthesis of3-(3,5-dimethylphenyl)-1-[3-(2,6-dimethylphenyl)phenyl]-2-ethoxy-2H-imidazo[4,5-b]pyrazine

The crude product mixture of the former reaction step and 135 g (0.91mol) of triethyl orthoformate are heated up under argon at 100° C.during two hours. The brown solution is filtered through a layer ofHyflo® filter aid and the filter aid rinsed with 10 ml of triethylorthoformate. The filtrate is concentrated under vacuum and dissolved in80 ml of hot heptane giving a turbid solution which is further filteredthrough a layer of Hyflo® filter aid followed by rinsing the filter aidwith heptane. The filtrate is concentrated under vacuum giving the titleproduct as off-white solid (yield: 6.1 g (59%)).

¹H-NMR (400 MHz, d₆-DMSO): δ=0.89 (t, 3H), 2.03 (s, 3H), 2.05 (s, 3H),2.32 (s, 6H), 3.18 (q, 2H), 6.83 (s, 1H), 6.96 (d, 1H), 7.11-7.23 (m,3H), 7.49-7.59 (m, 3H), 7.68 (s, 2 H), 7.74 (s, 1H), 7.83 (s, 1H),8.22-8.28 (m, 1H).

e) Synthesis of Complex (A-15)

3.0 g (6.7 mmol) of3-(3,5-dimethylphenyl)-1-[3-(2,6-dimethylphenyl)-phenyl]-2-ethoxy-2H-imidazo[4,5-b]pyrazineand 0.56 g (0.83 mmol) of chloro(1,5-cyclooctadiene)iridium(I) dimer aresuspended under argon in 25 ml of o-xylene.

The suspension is three times evacuated and backfilled with argon,followed by heating at 126° C. during 18 hours. The brown suspension iscooled down to room temperature, diluted with 50 ml of heptane andfiltered. The solid is three times suspended in 20 ml of ethanolfollowed by filtration and washing of the solid with ethanol, and afinal washing with heptane.

The resulting solid is dried under vacuum at 50° C., suspended in 30 mlof ethyl acetate followed by irradiation in an ultrasonic bath during 30minutes. The yellow solid is separated and suspended in 20 ml of2-butanone and 3 ml of 1M HCl. The suspension is heated at 100° C.during 30 hours, followed by filtration and washing with ethanol andheptane. The solid is dried under vacuum at 50° C. giving the titleproduct as a yellow solid (yield: 0.75 g (32%)).

APCI-LC-MS (positive, m/z): exact mass of C₈₁H₆₉IrN₁₂=1402.54; found1403.4 [M+1]⁺.

¹H-NMR (400 MHz, CDCl₃): δ=1.89 (s, 9H), 2.15 (s, 9H), 2.17 (s, 9H),2.40 (s, 9H), 6.02 (s, 3H), 6.42 (s, 3H), 6.67-6.74 (m, 3H), 6.90 (d,3H), 7.06 (s, 3H), 7.09-7.22 (m, 9H), 8.06 (d, 3H), 8.19 (d, 3H), 8.58(d, 3H).

Synthesis Example 3. Synthesis of Complex (B-15)

a) Synthesis of Complex Intermediate (I-1)

5.27 g (7.85 mmol) of chloro(1,5-cyclooctadiene)iridium(I) dimer aresuspended in 250 ml of toluene and three times evacuated and backfilledwith argon. 5.00 g (15.7 mmol) of2-ethoxy-1,3-diphenyl-2H-imidazo[4,5-b]pyrazine are added in smallportions at 66° C. during 20 minutes. Heating is continued at 66° C. andthe generated ethanol continuously removed by using a distillationbridge. The yellow-brown suspension is cooled down to room temperatureand diluted with 200 ml of ethanol, and cooling is continued until 5° C.is reached. Stirring is continued at this temperature for 30 minutes,followed by filtration and washing with 50 ml of cold ethanol and 50 mlof heptane. The resulting solid is dried under vacuum giving the titleproduct as a yellow solid (yield: 4.1 g (43%)).

¹H-NMR (400 MHz, CDCl₃): •=1.31-1.42 (m, 2H), 1.43-1.64 (m, 4H),1.73-1.86 (m, 2H), 2.50-2.59 (m, 2H), 4.68-4.78 (m, 2H), 7.57-7.69 (m,6H), 8.15-8.22 (m, 4H), 8.33 (s, 2H).

b) Synthesis of Complex (B-15)

1.9 g (3.1 mmol) of intermediate complex (I-1) and 2.69 g (5.97 mmol) of3-(3,5-dimethyl-phenyl)-1-[3-(2,6-dimethylphenyl)phenyl]-2-ethoxy-2H-imidazo[4,5-b]pyrazineare dissolved under argon in 130 ml of toluene. The yellow-brownsolution is three times evacuated and backfilled with argon, followed byheating at 107° C. during 21 hours. Toluene is distilled off andreplaced by 90 ml of o-xylene, and heating continued at 133° C. duringsix hours. The yellow-brown solution is diluted with 200 ml of heptane,filtered and the filtrate concentrated under vacuum. The dark resin issuspended in ethanol, filtered, and washed with ethanol and heptane. Theyellow solid is suspended in ethyl acetate, filtered, washed with ethylacetate and heptane, and further purified by chromatography (silica gel,heptane/ethyl acetate 7:3), giving the title product as a bright yellowsolid (yield: 0.19 g (5%)).

APCI-LC-MS (positive, m/z): exact mass of C₇₁H₅₇IrN₁₂=1270.45; found1271.3 [M+1]⁺.

¹H-NMR (400 MHz, CDCl₃): δ=1.73-1.88 (s and br. s, 6H), 2.10 (s, 3H),2.14 (s, 3H), 2.17 (s, 3H), 2.23 (s, 3H), 2.33 (br. s, 3H), 2.42 (s,3H), 5.96 (br. s, 1H), 6.06 (s, 1H), 6.43-7.36 (m, 23H), 8.04 (d, 1H),8.07 (d, 1H), 8.11 (d, 1H), 8.18 (d, 1H), 8.23 (d, 1H), 8.32 (d, 1H),8.54 (d, 1H), 8.62 (d, 1H), 8.76-8.81 (d, 1H).

Synthesis Example 4. Synthesis of Complex (A-17) a) Synthesis of2-bromo-1,3-diisopropyl-benzene

181 ml of 47% HBr solution (1.57 mol) are slowly added to 35.5 g (0.20mol) of 2,6-diiodopropylaniline at room temperature during 15 minutes.The white suspension is cooled down to −56° C. and 23.6 g (0.34 mol) ofsodium nitrite are added in portions during 10 minutes and stirringcontinued at the same temperature during one hour. 250 ml of ice-colddiethyl ether are slowly added during 10 minutes and the temperature letslowly rising to −15° C. during two hours until no more gas evolved. Thetemperature is decreased again to −56° C. and 24 ml of water are addedfirst followed by the addition of 118.5 g (0.41 mol) of sodium carbonatedecahydrate giving a brown suspension. The temperature is let raising toroom temperature during three hours with evolution of gas starting at−32° C. The resulting orange suspension is further stirred at roomtemperature during 16 hours. The water phase is separated and theorganic phase three times washed with water, dried and concentratedunder vacuum. Further purification is done by chromatography (silicagel, heptane) giving the title product as colorless oil (yield: 38.7 g(80%)).

¹H-NMR (400 MHz, CDCl₃): δ=1.33 (d, 12H), 3.54-3.66 (m, 2H), 7.19-7.23(m, 2H), 7.30-7.35 (m, 1H).

b) Synthesis of 1,3-diisopropyl-2-(3-nitrophenyl)benzene

4.07 g (24.4 mmol) of 3-nitrobenzeneboronic acid, 5.0 g (20.7 mmol) of2-bromo-1,3-diisopropyl-benzene, 21.3 g (0.10 mol) of tripotassiumphosphate, 248 mg (0.60 mmol) of2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl, and 45 mg (0.20 mmol)of palladium(II) acetate are suspended in 50 ml of toluene, and threetimes evacuated and backfilled with argon. The beige suspension isheated under reflux during 19 hours and 0.75 ml of water are added.Heating is continued under reflux during eight hours and the hotsuspension filtered through a 3 cm layer of Hyflo® filter aid followedby rinsing the filter aid with 200 ml of toluene. The filtrate is threetimes extracted with 200 ml of water, the organic phase dried oversodium sulfate, and concentrated under vacuum.

The resulting solid is suspended in heptane, filtered and dried undervacuum, and further purified by chromatography (silica gel,heptane/ethyl acetate 95:5), giving the title product as a light yellowsolid (yield: 3.8 g (67%)).

¹H-NMR (400 MHz, CDCl₃): δ=1.11 (d, 6H), 1.13 (d, 6H), 2.45-2.57 (m,2H), 7.27 (d, 2 H), 7.40-7.46 (m, 1H), 7.53-7.58 (m, 1H), 7.61-7.67 (m,1H), 8.09-8.13 (m, 1H), 8.25-8.30 (m, 1H).

c) Synthesis of 3-(2,6-diisopropylphenyl)aniline

11.0 g (38.8 mmol) of 1,3-diisopropyl-2-(3-nitrophenyl)benzene and 1.0 gof 5 wt %-palladium on carbon are reacted under 3 bar hydrogen pressureat 35° C. during six hours. The reaction mixture is filtered through a 3cm layer of Hyflo® filter aid and rinsed with additional ethanol,followed by concentration under vacuum. The beige solid is furtherpurified by recrystallization from heptane giving the title product as awhite solid (yield: 9.1 g (93%)).

¹H-NMR (400 MHz, CDCl₃): δ=1.11 (d, 6H), 1.13 (d, 6H), 2.67-2.79 (m,2H), 3.71 (br. s, 2H), 6.51-6.55 (m, 1H), 6.58-6.62 (m, 1H), 6.69-6.74(m, 1H), 7.18-7.25 (m, 3H), 7.32-7.38 (m, 1H).

d) Synthesis ofN2-[3-(2,6-diisopropylphenyl)phenyl]-N3-(3,5-dimethyl-phenyl)pyrazine-2,3-diamine

5.5 g (21.7 mmol) of 3-(2,6-diisopropylphenyl)aniline, 5.07 g (21.7mmol) of 3-chloro-N-(3,5-dimethylphenyl)pyrazin-2-amine, 0.10 g (0.11mmol) of tris(dibenzylidene-acetone)dipalladium(0), and 0.20 g (0.32mmol) of 2,2′-bis(diphenylphosphino)-1,1′-binaphthalene, and 2.92 g(30.4 mmol) of sodium tert-butoxide are suspended in 80 ml of toluene atroom temperature under argon. The brown suspension is three timesevacuated and backfilled with argon, followed by heating under refluxfor nine hours. The brown suspension is cooled down to room temperatureand diluted with 20 ml of water followed by filtration through a 3 cmlayer of Hyflo® filter aid and rinsing the filter aid with toluene. Thefiltrate is three times extracted with 50 ml of water, followed byextraction with 50 ml of 5% aqueous ammonia solution, and two times with50 ml of water. The organic phase is dried over sodium sulfate andconcentrated under vacuum giving a solid which is further stirred in 200ml of hot ethanol. Filtration and washing with cold ethanol gives thetitle product as light beige solid (yield: 7.3 g (75%)).

¹H-NMR (400 MHz, CDCl₃): δ=1.09 (d, 6H), 1.11 (d, 6H), 2.30 (s, 6H),2.65-2.77 (m, 2 H), 6.20 (s, 1H), 6.29 (s, 1H), 6.71 (s, 1H), 6.84-6.94(m, 3H), 7.08 (s, 1H), 7.19-7.24 (m, 2H), 7.33-7.40 (m, 3H), 7.76-7.83(m, 2H).

e) Synthesis of[3-(2,6-diisopropylphenyl)phenyl]-[3-(3,5-dimethylanilino)pyrazin-2-yl]-ammoniumchloride

A suspension of 5.0 g (11.1 mmol) ofN2-[3-(2,6-diisopropyl-phenyl)phenyl]-N3-(3,5-dimethylphenyl)pyrazine-2,3-diamineand 100 ml of 37% hydrochloric acid is stirred at room temperatureduring 22 hours. The resulting beige suspension is filtered and thesolid washed with 37% hydrochloric acid and hexane, and dried afterwashing on the filter funnel under vacuum, giving the title product as abeige solid (yield: 5.39 g (>99%)).

¹H-NMR (400 MHz, d₆-DMSO): δ=1.07 (t, 12H), 2.27 (s, 6H), 2.61-2.73 (m,2H), 6.68 (s, 1H), 6.78 (d, 1H), 7.22 (d, 2H), 7.28-7.43 (m, 4H),7.69-7.75 (m, 1H), 8.88 (br. s, 1H), 8.96 (br. s, 1H).

f) Synthesis of1-[3-(2,6-diisopropylphenyl)phenyl]-3-(3,5-dimethylphenyl)-2-ethoxy-2H-imidazo[4,5-b]pyrazine

A yellow suspension of 7.0 g (14.4 mmol) of[3-(2,6-diisopropyl-phenyl)phenyl]-[3-(3,5-dimethylanilino)pyrazin-2-yl]ammoniumchloride and 135 g (0.91 mol) of triethyl orthoformate is heated upunder argon at 100° C. during two hours. The resulting brown solution isfiltered and the small amount of solid residue rinsed with 10 ml oftriethyl orthoformate. The filtrate is concentrated under vacuum,dissolved in 80 ml warm heptane and filtered through a layer of Hyflo®filter aid and the filter aid rinsed with a small amount of heptane. Thesolution is cooled down to ice-bath temperature and the resultingsuspension stirred during one hour, followed by filtration and washingwith cold heptane, giving the title product as off-white solid (yield4.2 g (58%)).

¹H-NMR (400 MHz, d₆-DMSO): δ=0.88 (t, 3H), 0.99-1.18 (br. d, 12H), 2.32(s, 6H), 2.54-2.71 (m, 2H), 3.13-3.25 (m, 2H), 6.84 (s, 1H), 6.93-7.03(m, 1H), 7.19-7.31 (m, 2H), 7.31-7.42 (m, 1H), 7.43-7.61 (m, 3H),7.62-7.92 (m, 4H), 8.13-8.32 (m, 1H).

g) Synthesis of Complex (A-17)

3.0 g (5.9 mmol) of1-[3-(2,6-diisopropylphenyl)phenyl]-3-(3,5-dimethylphenyl)-2-ethoxy-2H-imidazo[4,5-b]pyrazineand 0.50 g (0.74 mmol) of chloro(1,5-cyclooctadiene)iridium(I) dimer aresuspended under argon in 25 ml of o-xylene.

The suspension is three times evacuated and backfilled with argon,followed by heating at 137° C. during 21 hours. The brown solution iscooled down to room temperature and diluted with 200 ml of ethanolfollowed by stirring at ice-bath temperature during 30 minutes. Theresulting suspension is filtered and the solid two times washed with 50ml of ethanol followed by washing with additional ethanol and 30 ml ofheptane. The yellow solid is dissolved in dichloromethane and filteredthrough a 3 cm layer of silica gel and the silica gel layer rinsed with20 ml of dichloromethane. The collected dichloromethane fractions arediluted with 25 ml of ethanol and the solution slowly concentrated undervacuum until precipitation occurred. The resulting solid is filtered offand washed with ethanol and heptane, and further purified bychromatography (silica gel, heptane/ethyl acetate), giving the titleproduct as yellow solid (yield: 0.8 g (35%)).

APCI-LC-MS (positive, m/z): exact mass of C₉₃H₉₃IrN₁₂=1570.73; found1571.7 [M+1]⁺.

¹H-NMR (400 MHz, CDCl₃): δ=1.00 (d, 9H), 1.15 (d, 9H), 1.16 (d, 18H),1.77 (s, 9H), 2.45 (s, 9H), 2.86-3.04 (m, 6H), 6.12 (s, 3H), 6.48 (s,3H), 6.69-6.76 (m, 3H), 6.79-6.90 (m, 6H), 7.21-7.32 (m, 6H), 7.34-7.41(m, 3H), 8.07 (d, 3H), 8.18 (d, 3H), 8.68 (d, 3H).

Synthesis Example 5. Synthesis of Complex (B-43)

1.30 g (2.15 mmol) of intermediate complex (I-1) and 2.07 g (4.09 mmol)of1-[3-(2,6-diisopropylphenyl)phenyl]-3-(3,5-dimethylphenyl)-2-ethoxy-2H-imidazo[4,5-b]pyrazineare dissolved under argon in 130 ml of toluene. The yellow-brownsolution is three times evacuated and backfilled with argon, followed byheating at 107° C. during 2 hours.

Some toluene is distilled off and replaced by 25 ml of o-xylene andheating continued at 133° C. during 17 hours. The yellow-brown solutionis diluted with 200 ml of heptane and filtered. The solution is filteredthrough a 3 cm layer of Hyflo® filter aid and the filter aid rinsed withtoluene, followed by concentration under vacuum. Further purification isdone by chromatography (silica gel, heptane/ethyl acetate). The isolatedsolid is dissolved in 10 ml of dichloromethane, 20 ml of ethanol areadded, and the resulting solution slowly concentrated under vacuum untilprecipitation occurs. The suspension is stirred during 30 minutes andfiltered. Dissolution and precipitation using dichloromethane andethanol is repeated twice, followed by filtration and drying undervacuum, giving the title product as a bright yellow solid (yield: 0.37 g(14%)).

APCI-LC-MS (positive, m/z): exact mass of C₇₉H₇₃IrN₁₂=1382.57; found1383.6 [M+1]+.

¹H-NMR (400 MHz, CDCl₃): δ=0.96 (d, 6H), 1.04-1.32 (m, 18H), 1.70 (s,3H), 1.74 (br. s, 3H), 2.40 (br. s, 3H), 2.46 (s, 3H), 2.68-2.80 (m,1H), 2.92-3.08 (m, 2H), 3.70-3.80 (m, 1 H), 5.98 (br. s, 1H), 6.13 (s,1H), 6.3-7.44 (m, 22H), 8.04 (d, 1H), 8.07 (d, 1H), 8.12 (d, 1 H), 8.17(d, 1H), 8.20 (d, 1H), 8.33 (d, 1H), 8.59 (d, 1H), 8.72 (d, 1H),8.77-8.83 (m, 1 H).

Synthesis Example 6. Synthesis of Bromo-Complex Intermediate (HI-1)

3.22 g (3.2 mmol) of iridium complex (see synthesis in WO2011/073149,example fac-EM1) are dissolved in 350 ml of dichloromethane. 3.42 g(19.2 mmol) of N-bromosuccinimide are added to the solution and thereaction is stirred under argon atmosphere at room temperature underexclusion of light. The progress is monitored via HPLC andN-bromosuccinimide (1.71 g 9.6 mmol) is added every two days until fullconversion of the starting material into the desired product isachieved. After completion, 160 mL of a 10% water solution of sodiummetabisulfite are added and the mixture is stirred for 3 hours. Thephases are separated and the organic solution is extracted with waterand dried over magnesium sulphate. The title product is isolated afterprecipitation in cyclohexane from dichloromethane as a yellow solid(yield: 3.64 g (92%)).

¹H-NMR (400 MHz, CD₂Cl₂): δ=8.92 (d, 3H, J=1.8 Hz), 8.37 (d, 3H, J=2.8Hz), 8.11 (d, 3H, J=2.8 Hz), 7.80-5.95 (m, 21H).

Synthesis Example 7. Synthesis of Iodo-Complex Intermediate (HI-2)

200 mg (0.20 mmol) of iridium complex (see synthesis in WO2011/073149,example fac-EM1) is dissolved in 20 ml of dichloromethane at roomtemperature and 268 mg (1.20 mmol) of N-iodosuccinimide are added. Thereaction mixture is stirred at room temperature for 48 hours, thesolvent is removed under vacuum and further purified by chromatography(silica gel, dichloromethane/ethyl acetate 9:1) giving the title product(yield 88%). ¹H-NMR (400 MHz, CD₂Cl₂): δ=9.08 (s, 1H), 8.37 (d, 1H),8.10 (d, 1H), 8.00 (broad signal, 4H), 7.11 (d, 1H), 6.42 (d, 1H), 6.86(t, 1H).

Synthesis Example 8. Synthesis of Bromo-Complex Intermediate (HI-3)

0.73 g (0.62 mmol) of iridium complex (see synthesis in EP13162776.2,Synthesis of complex BE-12) and 0.27 g (0.94 mmol) of1,3-dibromo-5,5-dimethylhydantoin are suspended in 100 mldichloromethane at room temperature. The suspension is stirred at 0° C.for 24 hours. The reaction mixture is treated with aqueous sodiumthiosulfate and the temperature raised to 20° C. The organic phase istwo times washed with water and dried over sodium sulfate and filtered.The light yellow solution is poured into 200 ml of methanol and theresulting suspension further stirred at ice-bath temperature. The lightyellow suspension is filtered and the solid washed with methanolfollowed by drying under vacuum, giving the title product as a lightyellow solid (yield: 0.74 g (84%)).

APCI-LC-MS (positive, m/z): exact mass of C₆₃H₄₈Br₃IrN₁₂=1402.13; found1405.3.

¹H-NMR (400 MHz, CD₂Cl₂): δ=1.88-2.11 (m, 12H), 2.70-2.95 (m, 6H),3.14-3.31 (m, 6 H), 6.27-7.37 (br. m, 21H), 8.93 (d, 3H).

Example 9. Synthesis of Complex (E-1)

NaOH (0.144 g of a 50% water solution), 50 ml of 1,4-dioxane and 50 mlof xylene are mixed together under argon atmosphere. Successivelybromo-complex product (HI-1) of synthesis example 6 (0.25 g, 0.2 mmol)is added and argon is bubbled through the solution for 15 minutes. Afteradding 3,5-dimethylphenylboronic acid (0.18 g, 1.2 mmol) andbis(tri-t-butylphosphine)palladium(0) (11 mg, 0.021 mmol), the solutionis purged for another 15 minutes with argon and then heated to 85° C.for 3 days. After completion, the reaction is cooled down to roomtemperature, the precipitate filtered and washed with 1,4-dioxane. Thesolid is dried under vacuum and dissolved in dichloromethane andextracted with water. The organic phase is dried over sodium sulfate,the solvent removed under vacuum and the resulting solid furtherpurified by column chromatography (silica gel, dichloromethan/ethylacetate 6/4). The title product is isolated as a yellow solid (yield:0.21 g (80%)).

¹H-NMR (400 MHz, CD₂Cl₂): δ*=8.57 (d, 3H, J=1.5 Hz), 8.36 (d, 3H, J=2.9Hz), 8.26 (d, 3H, J=2.9 Hz), 7.55-6.21 (m, 30H), 2.17 (s, 9H), 2.08 (s,9H).

Synthesis Example 10. Synthesis of Complex (A-1)

Bromo-complex product (HI-1) of synthesis example 6 (0.30 g, 0.24 mmol),2,6-dimethylphenylboronic acid (0.16 g, 1.08 mmol), and K₃PO₄ (0.31 g,1.44 mmol) are suspended in 150 ml of toluene and 36 ml of water. Argonis bubbled through the solution for 30 minutes and thentris-(dibenzylidenacetone)-dipalladium(0) (10 mg, 0.01 mmol) and Sphos(18 mg, 0.04 mmol) are added. The solution is purged with argon for 15minutes and then heated to reflux under inert atmosphere overnight.After cooling to room temperature the precipitate is filtered andpurified via column chromatography (silica, dichloromethane/ethylacetate 9/1). The title product is isolated as yellow solid (yield: 0.22g (70%)).

¹H-NMR (400 MHz, CD₂Cl₂): δ=9.09 (d, 3H, J=1.8 Hz), 8.40 (d, 3H, J=2.9Hz), 8.09 (d, 3H, J=2.9 Hz), 7.60-6.21 (m, 30H), 2.39 (s, 18H).

Synthesis Example 11. Synthesis of Complex (C-125)

1.00 g (0.80 mmol) of bromo-complex product (HI-1) of synthesis example6, 0.50 g (3.68 mmol) o-tolylboronic acid, and 1.03 g (4.85 mmol) oftripotassium phosphate are suspended under argon in 50 ml of toluene.The suspension is three times evacuated and backfilled with argon andtreated with 9.0 mg (0.04 mmol) of palladium(II) acetate and 33.0 mg(0.08 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl. Thebeige-yellow suspension is heated at 94° C. during 2.5 hours, the turbidsolution cooled down to room temperature, diluted with 200 ml ofdichloromethane and filtered through a 3 cm layer of Hyflo® filter aid.The filtrate is concentrated under vacuum, dissolved in dichloromethaneand passed through a 4 cm layer of silica gel followed by rinsing thesilica gel layer with dichloromethane. 30 ml of ethanol are added anddichloromethane is slowly evaporated under vacuum until precipitationoccurs. The solid is filtered off, washed with ethanol and dried undervacuum. The resulting solid is dissolved in 75 ml of hot DMF, cooleddown to room temperature and diluted with 25 ml of ethanol providing asuspension which is filtered, and the solid washed with ethanol andheptane giving the title product as a yellow solid (yield: 0.83 g(81%)).

APCI-LC-MS (positive, m/z): exact mass of C₇₂H₅₁IrN₁₂=1276.40; found1277.1 [M+1]⁺.

¹H-NMR (400 MHz, CDCl₃): δ=2.42 (s, 9H), 6.25-7.56 (very broad signal,9H), 6.82-6.89 (t, 3H), 6.91 (s, 6H), 7.24-7.34 (m, 12H), 7.39-7.44 (m,3H), 8.09 (d, 3H), 8.30 (d, 3H), 8.85 (s, 3H).

Synthesis Example 12. Synthesis of Complex (C-126)

1.00 g (0.80 mmol) of bromo-complex product (HI-1) of synthesis example6, 0.56 g (3.73 mmol) 2-ethylphenylboronic acid, and 1.03 g (4.59 mmol)of tripotassium phosphate are suspended under argon in 50 ml of toluene.The suspension is three times evacuated and backfilled with argon andtreated with 9.0 mg (0.04 mmol) of palladium(II) acetate and 33.0 mg(0.08 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl. Thebrown-yellow suspension is heated at 76° C. during 30 minutes. Theresulting yellow suspension is cooled down to room temperature andfiltered through a 4 cm layer of silica gel followed by rinsing thesilica gel layer with dichloromethane. The filtrate is slowlyconcentrated under vacuum until dichloromethane is removed. The solutionis diluted with 50 ml of heptane and filtered.

The solid is washed with ethanol and heptane followed by drying undervacuum, giving the title product as a yellow solid (0.89 g (84%)).

APCI-LC-MS (positive, m/z): exact mass of C₇₅H₅₇IrN₁₂=1318.45; found1319.5 [M+1]⁺.

¹H-NMR (400 MHz, CDCl₃): δ=1.20 (t, 9H), 2.78 (q, 6H), 6.25-7.51 (verybroad signal, 9 H), 6.86 (t, 3H), 6.92 (s, 6H), 7.23-7.44 (m, 12H), 8.09(s, 3H), 8.29 (s, 3H), 8.86 (s, 3 H).

Synthesis Example 13. Synthesis of Complex (C-127)

2.00 g (1.61 mmol) of bromo-complex product (HI-1) of synthesis example6, 1.22 g (7.44 mmol) 2-isopropylphenylboronic acid, and 2.05 g (9.66mmol) of tripotassium phosphate are suspended under argon in 100 ml oftoluene. The suspension is three times evacuated and backfilled withargon and treated with 18.0 mg (0.08 mmol) of palladium(II) acetate and66.0 mg (0.16 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl.The brown-yellow suspension is heated at 74° C. during 45 minutes,cooled down to room temperature, diluted with 150 ml of dichloromethaneand filtered through a 3 cm layer of Hyflo® filter aid. The filtered isrinsed with 200 ml of dichloromethane and the filtrated concentrated to50 ml volume. 50 ml of ethanol are added and the resulting suspensionfiltered and the solid washed with ethanol and heptane. 1.50 g of ayellow solid are obtained which are reacted again under the sameconditions as before with 0.31 g (1.89 mmol) 2-isopropylphenylboronicacid, 0.51 g (2.40 mmol) of tripotassium phosphate, 9.0 mg (0.04 mmol)of palladium(II) acetate, 33.0 mg (0.08 mmol) of2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl and 50 ml of toluene.The reaction mixture is heated at 76° C. during three hours, followed bywork-up and purification as described before, giving the title productas a light yellow solid (yield: 1.68 g (77%)).

APCI-LC-MS (positive, m/z): exact mass of C₇₈H₆₃IrN₁₂=1360.49; found1361.5 [M+1]⁺.

¹H-NMR (400 MHz, CD₂Cl₂): δ•=1.19 (d, 9H), 1.29 (d, 9H), 3.28-3.41 (m,3H), 6.14-7.55 (very broad signal, 15H), 6.89 (s, 6H), 7.21-7.30 (t,3H), 7.32-7.41 (d, 6H), 7.41-7.49 (d, 3H), 8.10 (s, 3H), 8.32 (s, 3H),8.82 (s, 3H).

Synthesis Example 14. Synthesis of Complex (G-1)

1.00 g (0.80 mmol) of bromo-complex product (HI-1) of synthesis example6, 0.70 g (3.69 mmol) 2-(trifluoromethyl)phenylboronic acid, and 1.03 g(4.59 mmol) of tripotassium phosphate are suspended under argon in 50 mlof toluene. The suspension is three times evacuated and backfilled withargon and treated with 9.0 mg (0.04 mmol) of palladium(II) acetate and33.0 mg (0.08 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl.The brown-yellow suspension is heated at 93° C. during 15 minutes. Theresulting beige-yellow suspension is cooled down to room temperature andfiltered. The solid is washed with toluene and ethanol and three timeswashed with water, filtered, and washed again with ethanol. Theresulting solid is dissolved in 75 ml of hot DMF and filtered through a3 cm layer of Hyflo® filter aid followed by rinsing the filter aid witha small amount of DMF. The filtrate is cooled down to room temperatureand diluted with 30 ml of ethanol. The suspension is filtered and theresulting solid washed with DMF, ethanol and heptane and further driedunder vacuum giving the title product as a yellow solid (yield: 0.83 g(76%)).

APCI-LC-MS (positive, m/z): exact mass of C₇₂H₄₂F₉IrN₁₂=1438.31; found1439.1 [M+1]⁺.

¹H-NMR (400 MHz, CD₂Cl₂): δ*=6.08-7.75 (very broad signal, 15H), 6.88(s, 6H), 7.47-7.68 (m, 9H), 7.80 (d, 3H), 8.10 (br. s, 3H), 8.31 (br. s,3H), 8.83 (s, 3H).

Synthesis Example 15. Synthesis of Complex (A-85)

0.73 g (0.52 mmol) of bromo-complex product (HI-3) of synthesis example8, 0.28 g (2.06 mmol) o-tolylboronic acid, and 0.55 g (2.59 mmol) oftripotassium phosphate are suspended under argon in 30 ml of toluene.The suspension is three times evacuated and backfilled with argon andtreated with 5.8 mg (0.03 mmol) of palladium(II) acetate and 21.3 mg(0.05 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl. Thebrown suspension is heated at 100° C. during 20 hours and cooled down toroom temperature. 1 g of sodium cyanide is dissolved in 20 ml warm waterand poured into the reaction mixture. The reaction mixture and purifiedas described for complex C-126, giving the title product as a lightyellow solid (yield: 0.36 g (48%)).

APCI-LC-MS (positive, m/z): exact mass of C₈₄H₆₉IrN₁₂=1438.54; found1439.7.

¹H-NMR (400 MHz, CD₂Cl₂): δ=1.86-2.10 (m, 12H), 2.46 (s, 9H), 2.70-2.95(m, 6H), 3.04-3.24 (m, 6H), 6.47-7.49 (br. m, 33H), 8.85 (s, 3H).

Synthesis Example 16. Synthesis of Complex (A-3)

Bromo-complex product (HI-1) of synthesis example 6 (0.30 g, 0.24 mmol),2,6-diisopropylphenylboronic acid (0.22 g, 1.08 mmol), and K₃PO₄ (0.31g, 1.44 mmol) are suspended in 180 ml of toluene and 36 ml of water.Argon is bubbled through the solution for 30 minutes and thentris-(dibenzylidenacetone)-dipalladium(0) (10 mg, 0.01 mmol) and Sphos(18 mg, 0.04 mmol) are added. The solution is purged with argon for 15minutes and then heated to reflux under inert atmosphere overnight.After cooling to room temperature, phases are separated, the organicphase collected and the solvent removed. The solid is then purified viacolumn chromatography (silica, cyclohexane/ethyl acetate). The titleproduct is isolated as yellow solid (yield: 0.27 g (67%)).

¹H-NMR (400 MHz, CD₂Cl₂): δ=8.64 (d, 3H, J=1.6 Hz), 8.25 (d, 3H, J=2.9Hz), 8.05 (d, 3H, J=2.9 Hz), 7.47-7.30 (m, 6H), 7.21 (t, 6H, J=7.5),7.16-7.00 (br m, 3H), 6.87 (d, 3H, J=7.4 Hz), 6.78 (t, 3H, J=7.5 Hz),6.74 (d, 3H, J=7.6 Hz), 6.65-6.20 (br m, 6H), 3.00 (sep, 3H, J=6.9),2.77 (sep, 3H, J=6.9 Hz), 1.20-1.12 (m, 18H), 1.10 (d, 9H, J=6.9 Hz),1.01 (d, 9H, J=6.9 Hz).

Synthesis Example 17. Synthesis of Complex (A-14)

Bromo-complex product (HI-1) of synthesis example 6 (0.20 g, 0.16 mmol),2,6-dimethylphenylboronic acid (0.18 g, 0.72 mmol), and K₃PO₄ (0.21 g,0.96 mmol) are suspended in 120 ml of toluene and 24 ml of water. Argonis bubbled through the solution for 30 minutes and thentris-(dibenzylidenacetone)-dipalladium(0) (7 mg, 0.01 mmol) and Sphos(12 mg, 0.03 mmol) are added. The solution is purged with argon for 15minutes and then heated to reflux under inert atmosphere overnight.After cooling to room temperature, phases are separated, the organicphase collected and the solvent removed. The solid is then purified viacolumn chromatography (silica, cyclohexane/ethyl acetate). The titleproduct is isolated as yellow solid (yield: 0.25 g (97%)).

¹H-NMR (400 MHz, CD₂Cl₂): δ=8.62 (d, 3H, J=1.4 Hz), 8.24 (d, 3H, J=2.9Hz), 8.04 (d, 3H, J=2.9 Hz), 7.41-7.18 (br m, 3H), 7.18-7.05 (m, 6H,J=7.5), 7.01 (s, 6H), 6.86 (d, 3H, J=7.4 Hz), 6.79 (t, 3H, J=7.6 Hz),6.73 (d, 3H, J=7.6 Hz), 6.65-6.20 (br m, 6H), 3.05-2.75 (m, 9H), 1.31(d, 6H, J=6.9 Hz), 1.18-1.14 (m, 18H), 1.10 (d, 9H, J=6.9 Hz), 0.97 (d,9H, J=6.9 Hz).

Synthesis Example 18. Synthesis of Complex (C-161) a) Synthesis of1-bromo-2-tert-butyl-benzene

176 ml of 48% HBr solution (1.57 mol) are slowly added to 30.5 g (0.20mol) of 2-tert-butylaniline at room temperature during 20 minutes. Thebeige suspension is cooled down to −56° C. and 23.8 g (0.34 mol) ofsodium nitrite are added in small portions during 20 minutes andstirring continued at the same temperature during one hour. 250 ml ofice-cold diethyl ether are slowly added during 15 minutes and thetemperature let slowly rising to −8° C. during two hours until no moregas evolved. The temperature is decreased again to −56° C. and 25 ml ofwater are added first followed by the addition of 118.5 g (0.41 mol) ofsodium carbonate decahydrate giving a brown suspension. The temperatureis let raising to room temperature during three hours with evolution ofgas starting at −28° C. The resulting brown suspension is furtherstirred at room temperature during 16 hours. The water phase isseparated and the organic phase three times washed with water, driedover sodium sulfate and concentrated under vacuum giving a brown oil.Further purification is done by chromatography (silica gel, heptane),followed by distillation of resulting oil under vacuum (97° C., 16mbbar), giving the title product as colorless oil (yield: 17.9 g (41%)).

¹H-NMR (400 MHz, CDCl₃): δ=1.58 (s, 9H), 7.07 (dt, 1H), 7.29 (dt, 1H),7.50 (dd, 1H), 7.64 (dd, 1H).

b) Synthesis of (2-tert-butylphenyl)boronic acid

33.0 ml (87 mmol) of 2.7M n-butyl lithium solution in heptane is slowlytreated at −73° C. with 16.0 g (72.8 mmol) of1-bromo-2-tert-butyl-benzene in 100 ml of THF under argon atmosphere,letting the temperature not rise above −70° C. Addition is completedafter 90 minutes, and stirring continued at −73° C. during one hour,giving a pink solution. 12.3 ml (109 mmol) of trimethylborate are slowlyadded during 75 minutes at −73° C., letting the temperature not riseabove −70° C. Stirring is continued at −73° C. during one hour first,and the temperature let raising to room temperature during three hours.The colorless solution is further stirred at room temperature during 16hours, followed by the slow addition of 30 ml of 10% aqueoushydrochloric acid solution during 10 minutes. Stirring is continued atroom temperature during 30 minutes, and THF distilled off under vacuumat 80° C., followed by the addition of 50 ml of heptane and stirring atice-bath temperature during one hour. The resulting suspension isfiltered and the solid washed with 20 ml of heptane, giving the titleproduct as an off-white solid (yield 7.7 g (58%)).

¹H-NMR (400 MHz, CDCl₃): δ=1.44 (s, 9H), 4.67 (s, 2H), 7.20 (td, 1H),7.32-7.40 (m, 2 H), 7.47 (d, 1H).

c) Synthesis of Complex (C-161)

3.00 g (2.41 mmol) of bromo-complex product (HI-1) of synthesis example6, 1.93 g (10.8 mmol) (2-tert-butylphenyl)boronic acid, and 3.07 g (14.5mmol) of tripotassium phosphate are suspended under argon in 700 ml oftoluene and 100 ml of water. The suspension is three times evacuated andbackfilled with argon and treated with 110 mg (0.12 mmol) oftris(dibenzylideneacetone)dipalladium(0) and 180 mg (0.44 mmol) of2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl. The red-brownsuspension is heated at 84° C. during three hours accompanied by a colorchange to yellow-brown, followed by direct filtration through a 3 cmlayer of Hyflo® filter aid, and rinsing the filter aid with plenty oftoluene. The toluene phase is separated and treated with 50 ml of 5%aqueous sodium cyanide solution and vigorously stirred during one hour,followed by the addition of 600 ml of dichloromethane. The mixture isfurther vigorously stirred at room temperature during 30 minutes, theorganic phase separated and dried over sodium sulfate. 20 ml of ethanolare added and the mixture filtered through a 3 cm layer of silica gelfollowed by rinsing the silica gel with dichloromethane. The solution isconcentrated under vacuum to ca. 50 ml volume and the precipitated solidseparated. followed by drying under vacuum, giving the title product asa yellow solid (yield: 2.02 g (60%)).

¹H-NMR (400 MHz, CD₂Cl₂): δ=1.06-1.41 (broad signal, 27H), 6.24-7.49(very broad signal, 30H), 7.59 (d, 3H), 8.08 (d, 3H), 8.28 (d, 3H), 8.77(br. s, 3H).

APCI-LC-MS (positive, m/z): exact mass of C₈₁H₆₉IrN₁₂=1402.54; found1403.2 [M+1]⁺.

Synthesis Example 19. Synthesis of Complex (C-130) a) Synthesis of(2-cyclohexylphenyl)boronic acid

46.7 ml (117 mmol) of 2.5M n-butyl lithium solution in hexane is slowlytreated at −73° C. with 24.0 g (97.3 mmol) of1-bromo-2-cyclohexyl-benzene in 200 ml of THF under argon atmosphere,letting the temperature not rise above −70° C. Addition is completedafter 90 minutes, giving a white suspension, and stirring continued at−73° C. during 30 minutes. 15.3 g (147 mmol) of trimethylborate areslowly added during 20 minutes at −73° C., letting the temperature notrise above −70° C. The colorless solution is further stirred at −74° C.during one hour, and the temperature let raising to room temperatureduring three hours. The colorless solution is further stirred at roomtemperature during 16 hours, followed by the slow addition of 30 ml of10% aqueous hydrochloric acid solution during 15 minutes. Stirring iscontinued at room temperature during three hours, and the reactionmixture two times extracted with 100 ml of ethyl acetate. The organicphase is dried over sodium sulfate, concentrated under vacuum, andfurther purified by chromatography (silica gel, heptane/ethyl acetate4:1), giving the title product as an off-white solid (yield: 10.1 g(51%)).

¹H-NMR (400 MHz, CDCl₃): δ=1.24-2.11 (m, 10H), 3.72-3.91 (m, 1H), 7.33(dt, 1H), 7.49 (d, 1H), 7.56 (dt, 1H), 8.26 (dd, 1H).

b) Synthesis of Complex (C-130)

1.00 g (0.80 mmol) of bromo-complex product (HI-1) of synthesis example6, 0.74 g (3.62 mmol) (2-cyclohexylphenyl)boronic acid, and 1.03 g (4.85mmol) of tripotassium phosphate are suspended under argon in 250 ml oftoluene and 50 ml of water. The suspension is three times evacuated andbackfilled with argon and treated with 36.8 mg (0.04 mmol) oftris(dibenzylideneacetone)dipalladium(0) and 59.5 mg (0.14 mmol) of2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl. The yellow suspensionis heated at 87° C. during three hours. The brown solution is cooleddown to room temperature, followed by filtration and extraction of theorganic phase with water (two times 100 ml). The organic phase is driedover sodium sulfate, concentrated under vacuum, and the resulting soliddissolved in dichloromethane. The solution is filtered through a 3 cmlayer of silica gel followed by rinsing the silica gel layer withdichloromethane, and addition of 30 ml of ethanol. The combined eluentsare diluted with 30 ml of ethanol and dichloromethane distilled offunder vacuum. The resulting suspension is filtered and the solid washedwith ethanol, and further purified by chromatography (silica gel,cyclohexane/ethyl acetate), giving the title product as an off-whitesolid (yield: 0.61 g (49%)).

¹H-NMR (400 MHz, CD₂Cl₂): δ=0.94-2.02 (m, 30H), 2.97 (m, 3H), 6.32-7.66(very broad signal, 12H), 6.84-6.97 (m, 9H), 7.24 (dt, 3H), 7.31-7.45(m, 9H), 8.10 (d, 3H), 8.32 (d, 3 H), 8.85 (d, 3H).

APCI-LC-MS (positive, m/z): exact mass of C₈₇H₇₅IrN₁₂=1480.59; found1481.7 [M+1]⁺.

Synthesis Example 20. Synthesis of Complex (C-128) a) Synthesis of2-isobutylaniline

14.59 g (0.60 mol) of magnesium shavings are suspended under argon in 50ml of tetrahydrofuran. 90.4 g (0.66 mol) of 1-bromo-2-methylpropane in200 ml of tetrahydrofuran are slowly added during 45 minutes bycarefully regulating the exothermy of the Grignard reaction by coolingwith an ice-bath keeping the reaction temperature at a maximum of 55° C.The grey suspension is further stirred during 50 minutes and allowed tocool down to room temperature, giving a grey-brown solution. A colorlesssolution of 40.89 g (0.30 mol) of anhydrous zinc chloride in 200 ml oftetrahydrofuran is added during 10 minutes and the released exothermycarefully regulated with an ice-bath keeping the temperature at amaximum of 39° C. The resulting grey thick suspension is further stirredduring 95 minutes until the temperature reaches 26° C., and slowly addedduring 30 minutes to a red-brown solution of 26.3 g (150 mmol) of2-bromoaniline, 1.31 g (3.00 mmol) of2-dicyclohexylphosphino-2′,6′-bis(N,N-dimethylamino)biphenyl (=CPhos),0.34 g (1.51 mmol) of palladium(II) acetate in 200 ml of THF, bycarefully controlling the exothermy at a maximum of 32° C. using awater-bath. 50 ml of water are first carefully added under coolingkeeping the temperature at a maximum of 33° C., followed by the additionof 500 ml of water and 200 ml of saturated ethylenediaminetetraaceticacid trisodium salt hydrate (EDTA-Na₃), and by stirring for 30 minutes.The suspension is filtered through a layer of Hyflo® filter aid and thefilter aid rinsed with 500 ml of toluene. The organic phase is separatedand washed with 100 ml of EDTA-Na₃ and 100 ml of saturated sodiumchloride, followed by drying over sodium sulfate and concentration undervacuum. The oil is further distilled (120° C., 0.1 mbar) giving thetitle product as a colorless oil (yield: 16.5 g (74%)).

¹H-NMR (400 MHz, CD₂Cl₂): δ=1.00 (d, 6H), 1.96 (dq, 1H), 2.42 (d, 2H),3.64 (br. s, 2H), 6.72 (m, 2H), 7.04 (m, 2H).

b) Synthesis of 1-bromo-2-isobutyl-benzene

88.0 ml (0.79 mol) of 48% HBr solution are slowly added to 14.9 g (0.10mol) of 2-isobutylaniline at room temperature during 15 minutes bycarefully controlling the temperature. The white suspension is cooleddown to −55° C. and 11.8 g (0.17 mol) of sodium nitrite are carefullyadded in small portions at a maximum temperature of −48° C. during 15minutes. 100 ml of ice-cold diethyl ether are slowly added to the darksuspension during 15 minutes and the suspension further stirred during90 minutes at −53° C. The temperature is slowly let rising first to 8°C. during 30 minutes carefully controlling the amount of gas evolution,then to room temperature during 75 minutes until no more gas evolved.The temperature is decreased again to −43° C. and 60 g (0.21 mol) ofsodium carbonate decahydrate are added. The temperature is let raisingto room temperature during one hour. The water phase is separated andthe organic phase diluted with 100 ml of heptane, then three timeswashed with water, dried over sodium sulfate and concentrated undervacuum giving a dark oil. Further purification is done by chromatography(silica gel, heptane), giving the title product as colorless oil (yield:5.3 g (25%)). GC-MS (CI): exact mass of C₁₀H₁₃Br=212.02; found 212.0[M]⁺.

c) Synthesis of (2-isobutylphenyl)boronic acid

10.5 ml (28.4 mmol) of 2.7M n-butyl lithium solution in heptane isslowly treated at −70° C. with 5.00 g (23.5 mmol) of1-bromo-2-isobutyl-benzene in 50 ml of THF under argon atmosphere,letting the temperature not rise above −70° C. Addition is completedafter 30 minutes, and stirring continued at −72° C. during 30 minutes,giving a colorless solution. 3.66 g (35.2 mmol) of trimethylborate areslowly added during one hour at −72° C., letting the temperature notrise above −68° C. The temperature is let raising to room temperatureduring two hours, and stirring continued for one hour. The colorlesssolution is slowly treated with 5 ml of water and 20 ml of 10% aqueoushydrochloric acid solution. THF is distilled off under vacuum, followedby the addition of 30 ml of heptane, and stirring at ice-bathtemperature during one hour. The resulting suspension is filtered andthe solid washed with a small amount of cold heptane, then dried undervacuum, giving the title product as an off-white solid (yield 1.75 g(42%)).

¹H-NMR (400 MHz, CDCl₃): δ=0.93 (dd, 6H), 1.89 (m, 1H), 2.71, 3.11 (2 d,2H), 6.32 (br. s, 2H), 7.16-7.40 (m, 2H), 7.45-7.58 (m, 1H), 8.23 (dd,1H).

d) Synthesis of Complex (C-128)

1.50 g (1.21 mmol) of bromo-complex product (HI-1) of synthesis example6, 1.29 g (7.25 mmol) (2-isobutylphenyl)boronic acid, and 1.54 g (7.25mmol) of tripotassium phosphate are suspended under argon in 70 ml oftoluene and 20 ml of water. The suspension is three times evacuated andbackfilled with argon and treated with 55 mg (0.06 mmol) oftris(dibenzylideneacetone)dipalladium(0) and 90 mg (0.22 mmol) of2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl. The light beigesuspension is heated at 83° C. during 22 hours followed by the additionof 0.30 g (1.69 mmol) of (2-isobutylphenyl)boronic acid. Heating iscontinued for five hours, 100 ml of toluene are added, followed bydirect filtration through a 3 cm layer of Hyflo® filter aid, and rinsingthe filter aid with plenty of toluene. The toluene phase is separatedand treated with 5% aqueous sodium cyanide solution, and the resultingmixture vigorously stirred during 30 minutes. The organic phase isseparated and washed with water, dried over sodium sulfate andconcentrated under vacuum. The yellow residue is dissolved indichloromethane and filtered through a 3 cm layer of silica gel followedby rinsing the silica gel layer with a dichloromethane/ethanol 95:5solvent mixture. Dichloromethane is distilled off under vacuum, theprecipitated solid filtered off, washed with ethanol and dried undervacuum. The solid is further purified by chromatography (silica gel,dichloromethane/methanol), giving the title product as a light yellowsolid (yield: 0.67 g (40%)).

¹H-NMR (400 MHz, CD₂Cl₂): δ=0.72 (d, 9H), 0.73 (d, 9H), 1.74 (m, 3H),2.62 (dd, 3H), 6.12-7.78 (very broad signal, 12H), 6.86 (m, 9H), 7.29(m, 9H), 7.36 (m, 3H), 8.10 (d, 3 H), 8.33 (d, 3H), 8.83 (d, 3H).

APCI-LC-MS (positive, m/z): exact mass of C₈₁H₆₉IrN₁₂=1402.54; found1403.6 [M+1]⁺.

Synthesis Example 21. Synthesis of Complex (A-6) a) Synthesis of(2-ethyl-6-methyl-phenyl)boronic acid

45.9 ml (115 mmol) of 2.5M n-butyl lithium solution in hexane is slowlytreated at −73° C. with 24.0 g (23.5 mmol) of 1-ethyl-2-iodotoluene in200 ml of THF under argon atmosphere, letting the temperature not riseabove −70° C. Addition is completed after 90 minutes, and stirringcontinued at −73° C. during one hour, giving a white suspension. 15.9 ml(142 mmol) of trimethylborate are slowly added during one hour at −73°C., letting the temperature not rise above −70° C. The temperature islet raising to room temperature during two hours (aspect: clear andcolorless solution), and stirring continued for 18 hours. The slightlyturbid solution is slowly treated with water by intermittent coolingwith an ice-bath, followed by the addition of 30 ml of 10% aqeuoushydrochloric acid solution at room temperature. The organic solvents aredistilled off at a bath-temperature of 80° C. Heptane is added and themixture stirred at 0° C. during one hour. The resulting suspension isfiltered and the solid washed with a small amount of ice-cold water andheptane, followed by drying under vacuum, giving the title product as anoff-white solid (yield: 12.9 g (81%)).

¹H-NMR (400 MHz, CDCl₃): δ=1.26 (t, 3H), 2.38 (s, 3H), 2.67 (q, 2H),5.03 (s, 2H), 7.01 (d, 1H), 7.05 (d, 1H), 7.05 (d, 1H), 7.21 (d, 1H).

Synthesis of Complex (A-6)

b) 1.00 g (0.80 mmol) of bromo-complex product (HI-1) of synthesisexample 6, 0.59 g (3.60 mmol) (2-ethyl-6-methyl-phenyl)boronic acid, and1.03 g (4.59 mmol) of tripotassium phosphate are suspended under argonin 50 ml of toluene. The suspension is three times evacuated andbackfilled with argon and treated with 9.0 mg (0.04 mmol) ofpalladium(II) acetate and 33.0 mg (0.08 mmol) of2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl. The brown-yellowsuspension is heated at 97° C. during 30 minutes, and five hours at 107°C. The brown suspension is cooled down to room temperature, diluted withdichloromethane and filtered over a 3 cm layer of silica gel followed byrinsing the silica gel with dichloromethane mixed with a small amount ofmethanol. Dichloromethane is removed under vacuum until precipitationstarted. The yellow suspension is filtered and the solid dried undervacuum. The isolated product (0.45 g) is reacted and worked up in asecond step under the same reaction conditions, with 0.20 g of(2-ethyl-6-methyl-phenyl)boronic acid, 5 mg of palladium(II) acetate, 16mg of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl and 0.50 g oftripotassium phosphate in 20 ml toluene, giving the title product as alight yellow solid (yield: 0.38 g (35%)).

¹H-NMR (400 MHz, CD₂Cl₂): δ=1.03-1.14 (m, 9H), 2.11, 2.19 (2 s, 9H),2.39-2.50 (m, 3 H), 2.53-2.65 (m, 3H), 6.17-7.84 (very broad signal,12H), 6.70-6.77 (m, 3H), 6.81-6.95 (2 m, 6H), 7.11-7.27 (m, 9H), 8.09(m, 3H), 8.29 (m, 3H), 8.64 (m, 3H).

APCI-LC-MS (positive, m/z): exact mass of C₇₈H₆₃IrN₁₂=1360.49; found1361.6 [M+1]⁺.

Synthesis Example 22. Synthesis of Complex (A-2) a) Synthesis of2-bromo-1,3-diethyl-benzene

265 g (1.57 mol) of 48% HBr solution are slowly added to 30.5 g (0.20mol) of 2,6-diethylaniline at room temperature during 15 minutes bycarefully controlling the temperature. The beige suspension is cooleddown to −55° C. and 23.8 g (0.34 mol) of sodium nitrite are carefullyadded in small portions at a maximum temperature of −48° C. during 40minutes. The brown suspension is further stirred at −53° C. during 50minutes. 250 ml of pre-cooled diethyl ether are slowly added during 15minutes and the temperature slowly increased to −18° C. during 30minutes until no more gas is released (careful control of gasevolution). The brown suspension is cooled down to −54° C. and slowlytreated with 25 g of water and 119 g (0.41 mol) of sodium carbonatedecahydrate. The temperature is let rising to room temperature duringfour hours carefully controlling the amount of gas released. Thesuspension is further stirred at room temperature during 19 hours. Theorganic phase is separated, extracted with water (2×100 ml), dried oversodium sulfated and concentrated under vacuum. The crude product isfurther purified by chromatography (silica gel, heptane) giving thetitle product as a yellow oil (yield: 36.3 g (83%)).

¹H-NMR (400 MHz, CD₂Cl₂): δ=1.35 (t, 6H), 2.91 (q, 4H), 7.17 (d, 2H),7.27 (dd, 1H).

b) Synthesis of (2,6-diethylphenyl)boronic acid

48.0 ml (0.12 mol) of 2.7M n-butyl lithium solution in heptane is slowlytreated at −73° C. with 22.0 g (0.10 mol) of 2-bromo-1,3-diethyl-benzenein 200 ml of THF under argon atmosphere, letting the temperature notrise above −70° C. Addition is completed after 70 minutes, and stirringcontinued at −73° C. during one hour, giving a white suspension. 15.7 g(0.15 mol) of trimethylborate are slowly added during 25 minutes at −73°C., letting the temperature not rise above −70° C. Stirring is continuedat −73° C. during one hour first, and the temperature let raising toroom temperature during two hours. The colorless solution is furtherstirred at room temperature during 16 hours, followed by the slowaddition of 30 ml of 10% aqueous hydrochloric acid solution during 15minutes. Stirring is continued at room temperature during 30 minutes,and THF distilled off under vacuum at 80° C., followed by the additionof 50 ml of heptane and stirring at ice-bath temperature during onehour. The resulting suspension is filtered and the solid washed with 30ml of heptane, giving the title product as an off-white solid.

¹H-NMR (400 MHz, CDCl₃): δ=1.27 (t, 6H), 2.69 (q, 4H), 4.73 (s, 2H),7.07 (d, 2H), 7.27 (t, 1H).

c) Synthesis of Complex (A-2)

1.00 g (0.80 mmol) of bromo-complex product (HI-1) of synthesis example6, 645 mg (3.62 mmol) (2,6-diethylphenyl)boronic acid, and 1.03 g (4.83mmol) of tripotassium phosphate are suspended under argon in 250 ml oftoluene and 50 ml of water. The suspension is three times evacuated andbackfilled with argon and treated with 37 mg (0.04 mmol) oftris(dibenzylideneacetone)dipalladium(0) and 60 mg (0.15 mmol) of2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl. The greenish brownsuspension is heated at 87° C. during six hours, directly filteredthrough a 3 cm layer of Hyflo® filter aid, and the filter aid rinsedwith plenty of toluene. The organic phase is extracted with water (2×100ml), dried over sodium sulfate and concentrated under vacuum. The solidresidue is dissolved in dichloromethane and filtered through a 3 cmlayer of silica gel followed by rinsing the silica gel withdichloromethane. The combined filtrates are treated with 30 ml ofethanol and dichloromethane distilled off under vacuum. The suspensionis filtered and the solid washed with ethanol and further purified bychromatography (silica gel, cyclohexane/ethyl acetate). The productfractions are collected and concentrated under vacuum untilprecipitation occurred. The solid is separated and washed withcyclohexane and ethanol, further dried under vacuum, giving the titleproduct as a light yellow solid (yield: 0.81 g (72%)).

¹H-NMR (400 MHz, CD₂Cl₂): δ=1.04-1.15 (m, 18H), 2.37-2.51 (m, 6H),2.51-2.65 (m, 6 H), 6.23-7.70 (very broad signal, 12H), 6.76 (dd, 3H),6.85 (t, 3H), 6.91 (d, 3H), 7.18 (t, 6 H), 7.28 (t, 3H), 8.09 (d, 3H),8.29 (d, 3H), 8.68 (d, 3H).

APCI-LC-MS (positive, m/z): exact mass of C₈₁H₆₉IrN₁₂=1402.54; found1403.6 [M+1]⁺.

Synthesis Example 23. Synthesis of Bromo-Complex Intermediate (HI-4)

1.00 g (1.0 mmol) of iridium complex (see synthesis in WO2011/073149,example fac-EM1) are dissolved in 100 ml of dichloromethane at roomtemperature under argon atmosphere. 1.60 mg (0.01 mmol) of iron(III)bromide are added first followed by the slow addition of 178 mg (1.0mmol) of N-bromosuccinimide in 100 ml of dichloromethane during 90minutes. Stirring is continued during 16 hours. 20 ml of ethanol areadded and the mixture filtered through a 3 cm layer of silica gel,followed by rinsing the silica gel with dichloromethane/EtOH 95:5eluent. The combined eluents are concentrated under vacuum and furtherpurified by chromatography (silica gel, dichloromethane/ethyl acetate).The combined product fractions are concentrated under vacuum and theresulting solid dissolved in dichloromethane, followed by the additionof ethanol. Dichloromethane is removed under vacuum and the resultingprecipitate filtered and further washed with ethanol, giving the titleproduct as a yellow solid (yield: 0.6 g (56%)).

¹H-NMR (400 MHz, CD₂Cl₂): δ=6.09-7.57 (very broad signal, 12H), 6.59 (d,1H), 6.65-6.74 (m, 3H), 6.83-6.92 (m, 3H), 6.96 (dd, 1H), 7.17-7.25 (m,3H), 8.11 (m, 3H), 8.38 (m, 3H), 8.81 (d, 2H), 8.95 (d, 1H).

APCI-LC-MS (positive, m/z): exact mass of C₅₁H₃₂BrIrN₁₂=1084.17; found1085.3 [M+1]⁺.

Synthesis Example 24. Synthesis of Complex (X-1)

150 mg (0.14 mmol) of the bromo complex intermediate (HI-4) of synthesisexample 23 are reacted according to synthesis example 20 d)(PM2119-isobutyl) with 43 mg (0.26 mmol) of (2-isopropylphenyl)boronicacid, 170 mg (0.80 mmol) of tripotassium phosphate, 6 mg (0.007 mmol) oftris(dibenzylideneacetone)dipalladium(0), and 10 mg (0.02 mmol) of2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl, in 20 ml of toluene and5 ml of water, with a reaction time of four hours at 88° C. Theresulting brown suspension is diluted with 10 ml of toluene and theorganic phase stirred with 5 ml of 5% aqueous sodium cyanide solution.The light yellow organic phase is separated and filtered through a 3 cmlayer of silica gel followed by rinsing the silica gel withdichloromethane. The combined eluents are concentrated under vacuum andthe resulting solid three times dissolved in 20 ml of dichloromethaneand 3 ml of ethyl acetate followed by removal of dichloromethane undervacuum until precipitation of a solid is each time initiated. Theresulting solid is washed with heptane and dried under vacuum, givingthe title product as a light yellow solid (yield: 122 mg (78%)).

¹H-NMR (400 MHz, CD₂Cl₂): δ=1.18 (d, 3H), 1.27 (d, 3H), 3.32 (m, 1H),6.21-7.58 (m and very broad signal, 27H), 8.06 (d, 1H), 8.10 (m, 2H),8.28 (d, 1H), 8.37 (dd, 2H), 8.81 (m, 3H).

APCI-LC-MS (positive, m/z): exact mass of C₆₀H₄₃IrN₁₂=1124.34 found1125.5 [M+1]⁺.

Synthesis Example 25. Synthesis of Complex (X-2)

200 mg (0.18 mmol) of the of the bromo complex intermediate (HI-4) ofsynthesis example 23 are reacted according to synthesis example 14 with69 mg (0.36 mmol) of (2-trifluoromethylphenyl)boronic acid, 230 mg (1.08mmol) of tripotassium phosphate, 2 mg (0.009 mmol) of palladium(II)acetate, and 8 mg (0.02 mmol) of2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl, in 20 ml of toluene,with a reaction time of five hours at 93° C. The resulting brownsuspension is diluted with 10 ml of and filtered through a 3 cm layer ofsilica gel followed by rinsing the silica gel with dichloromethane/ethylacetate 9:1 mixture. The combined eluents are concentrated under vacuumand the resulting yellow dissolved in 30 ml of dichloromethane and 10 mlof ethanol. Dichloromethan is removed under vacuum until precipitationstarts, giving the title product as a light yellow solid (yield: 64 mg(30%)).

¹H-NMR (400 MHz, CD₂Cl₂): δ=6.09-7.68 (br. signal, 12H), 6.73 (m, 2H),6.78-6.95 (m, 7 H), 7.21 (m, 2H), 7.52 (m, 2H), 7.63 (d, 1H), 7.80 (d,1H), 8.07 (d, 1H), 8.11 (t, 2H), 8.28 (d, 1H), 8.37 (dd, 2H), 8.78 (dd,1H), 8.83 (m, 2H).

APCI-LC-MS (positive, m/z): exact mass of C₅₈H₃₆F₃IrN₁₂=1150.28 found1551.4 [M+1]⁺.

Synthesis Example 26. Synthesis of Bromo-Complex Intermediate (HI-5)

0.50 g (0.50 mmol) of iridium complex (see synthesis in WO2011/073149,complex Em8) and 0.43 g (1.50 mmol) of 1,3-dibromo-5,5-dimethylhydantoinare suspended in 100 ml dichloromethane at room temperature. The yellowsolution is stirred during 23 hours and ethanol is added.Dichloromethane is removed under vacuum leading to precipitation of theproduct. The solid is separated and dried under vacuum, giving the titleproduct as a light yellow solid (yield: 0.53 g (86%)).

¹H-NMR (400 MHz, CDCl₃): δ=6.02-7.63 (broad signal, 8H), 6.31 (d, 1H),6.39 (d, 1H), 6.43 (m, 2H), 6.53 (d, 1H), 6.59 (dd, 2H), 6.83 (m, 3H),6.97 (m, 3H), 7.11 (t, 1H), 7.26 (dd, 1H), 7.38 (m, 1H), 8.10 (m, 4H),8.32 (d, 1H), 8.36 (d, 1H), 8.88 (d, 1H), 8.96 (d, 1H).

Synthesis Example 27. Synthesis of Complex (J-113)

300 mg (0.24 mmol) of the bromo complex intermediate (HI-5) of synthesisexample 26 are reacted according to synthesis example 20 d) with 178 mg(1.09 mmol) of (2-isopropylphenyl)boronic acid, 307 mg (1.45 mmol) oftripotassium phosphate, 11 mg (0.012 mmol) oftris(dibenzylideneacetone)dipalladium(0), and 18 mg (0.04 mmol) of2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl, in 30 ml of toluene and5 ml of water, with a reaction time of four hours at 88° C. Theresulting brown suspension is diluted with 10 ml of dichloromethane andthe organic phase stirred with 5 ml of 5% aqueous sodium cyanidesolution. The light yellow organic phase is separated and filteredthrough a 3 cm layer of silica gel followed by rinsing the silica gelwith dichloromethane. The combined eluents are concentrated under vacuumand the resulting solid separated and washed with ethanol and heptane,followed by drying under vacuum, giving the title product as a lightyellow solid (yield: 221 mg (67%)).

¹H-NMR (400 MHz, CDCl₃): δ=1.19 (m, 9H), 1.27 (m, 9H), 3.36 (m, 3H),6.30-7.70 (broad signal and m, 36H), 7.94 (d, 1H), 8.04 (d, 1H), 8.08(d, 1H), 8.15 (d, 1H), 8.23 (d, 1H), 8.77 (d, 1H), 8.84 (d, 1H).

Synthesis Example 28. Synthesis of Complex (L-1)

500 mg (0.40 mmol) of the bromo complex intermediate (HI-5) of synthesisexample 26 are reacted according to synthesis example 20 d) with 460 mg(2.42 mmol) of (2-trifluoromethylphenyl)boronic acid, 513 mg (2.42 mmol)of tripotassium phosphate, 18.5 mg (0.020 mmol) oftris(dibenzylideneacetone)dipalladium(0), and 30 mg (0.07 mmol) of2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl, in 40 ml of toluene and10 ml of water, with a reaction time of five hours at 88° C. Theresulting brown suspension is diluted with 30 ml of dichloromethane andthe organic phase stirred with 5 ml of 5% aqueous sodium cyanidesolution. The organic phase is separated and concentrated under vacuum.The solid residue is dissolved in 20 ml of dichloromethane and 10 ml oftoluene. Dichloromethane is distilled off and the suspension filtered,the solid washed with ethanol and heptane and dried under vacuum, givingthe title product as a light yellow solid (yield: 476 mg (82%)).

¹H-NMR (400 MHz, CD₂Cl₂): δ•=6.15-7.74 (very broad signal, 8H), 6.40 (d,1H), 6.52 (d, 1H), 6.59 (t, 1H), 6.74-6.96 (m, 8H), 7.16 (m, 3H), 7.31(m, 3H), 7.46-7.70 (m, 8H), 7.90 (m, 3H), 8.08 (m, 4H), 8.27 (dd, 2H),8.78 (s, 1H), 8.84 (s, 1H).

APCI-LC-MS (positive, m/z): exact mass of C₇₄H₄₄F₉IrN₁₀=1436.32; found1437.4 [M+1]⁺.

Synthesis Example 29. Synthesis of Complex (Y-1) a) Synthesis ofN2,N3-bis(4-ethylphenyl)pyrazine-2,3-diamine

27.9 g (0.19 mol) of 2,3-dichloropyrazine and 50.0 g (0.41 mol) of4-ethylaniline in 200 ml of mesitylene are heated at 164° C. duringthree hours. The black suspension is cooled down to room temperature,diluted with 50 ml of toluene and stirring continued during 90 minutes.The suspension is filtered and the solid washed with toluene andheptane. The solid is suspended in 500 ml of water, and 200 ml of 25%aqueous ammonia solution are added under stirring, and stirringcontinued for 30 minutes. The suspension is filtered and the solidwashed with water (2×250 ml), followed by washing with cyclohexane(2×200 ml). The solid is suspended in 400 ml of cyclohexane and heatedunder reflux during one hour, cooled down to room temperature andfurther stirred during one hour. The suspension is filtered and washedwith hexane and dried under vacuum, giving the title product as a lightyellow solid (yield: 28.3 g (47%)).

¹H-NMR (400 MHz, d₄-MeOD): δ=1.25 (t, 6H), 2.64 (q, 4H), 7.18 (d, 4H),7.46 (d, 6H).

b) Synthesis of [3-(4-ethylanilino)pyrazin-2-yl]-(4-ethylphenyl)ammoniumchloride

A yellow suspension of 28.3 g (88.9 mmol) ofN2,N3-bis(4-ethylphenyl)pyrazine-2,3-diamine and 300 ml of 37% aqueoushydrochloric acid solution is stirred at room temperature during onehour. The suspension is diluted with water and stirring continued. Thesuspension is filtered and the solid washed with 100 ml of water. Theyellow solid is three times suspended with 100 ml of cyclohexane andfiltered, followed by drying on the filter under vacuum first, followedby drying at room temperature in the vacuum oven during two days, givingthe title product as a light yellow solid (yield: 41.3 g, still wet).

¹H-NMR (400 MHz, d₆-DMSO): δ=1.20 (t, 6H), 2.61 (q, 4H), 7.24 (d, 4H),7.41 (s, 2H), 7.63 (d, 4H), 10.08 (br. s, 2H).

c) Synthesis of2-ethoxy-1,3-bis(4-ethylphenyl)-2H-imidazo[4,5-b]pyrazine

40.0 g (ca. 88 mmol, still including residual water) of[3-(4-ethylanilino)pyrazin-2-yl]-(4-ethylphenyl)ammonium chloride and300 ml (1.8 mol) of triethyl orthoformate heated under argon at 100° C.during 18 hours. The light orange solution is cooled down to roomtemperature and filtered. The filtrated is concentrated under vacuumgiving and the resulting suspension filtered and washed with heptane,giving the title product as a light pink solid (yield: 23.7 g).

¹H-NMR (300 MHz, d₆-DMSO): δ=0.89 (t, 3H), 1.20 (t, 6H), 2.61 (q, 4H),3.16 (q, 2H), 7.29 (d, 4H), 7.47 (s, 2H), 7.67 (s, 1H), 7.93 (m, 4H).

d) Synthesis of Complex Intermediate (Cl-1)

The reaction is conducted according to synthesis example 2 e), with 42.9g (0.11 mol) of2-ethoxy-1,3-bis(4-ethylphenyl)-2H-imidazo[4,5-b]pyrazine, 7.00 g (10.4mmol) of chloro(1,5-cyclooctadiene)iridium(I) dimer in 400 ml ofo-xylene, at 138° C. during eight hours. The resulting dark suspensionis poured into 1800 ml of methanol and stirred during 30 minutes. Thesuspension is filtered and the solid washed with 150 ml of methanol. Thesolid is dissolved in dichloromethane and filtered over silica gel (2×8cm filter) using a dichloromethane/toluene eluent with a small amount ofadded ethanol. The combined filtrates are diluted with 300 ml ofmethanol until precipitation started. The suspension is stirred for onehour, then filtered and the solid washed with methanol (3×15 ml),followed by drying under vacuum, giving the title product as a lightyellow solid (yield: 8.49 g (35%)).

e) Synthesis of Bromo-Complex Intermediate (HI-6)

The reaction is conducted according to synthesis example 8, with 1.30 g(1.11 mmol) of the product of the synthesis example 29 d), 483 mg (1.69mmol) of 1,3-dibromo-5,5-dimethylhydantoin in 100 ml of dichloromethaneat 0° C. during 17 hours, giving the title product as a light yellowsolid (yield: 1.52 g (97%)).

¹H-NMR (400 MHz, CD₂Cl₂): δ•=1.00 (m, 18H), 2.28 (q, 6H), 2.42 (m, 3H),2.66 (m, 3 H), 5.83-7.72 (2 very broad signals, 12H), 6.55 (s, 3H), 8.10(d, 3H), 8.39 (d, 3H), 8.92 (s, 3H).

f) Synthesis of Complex (Y-1)

760 mg (0.54 mmol) of the product HI-6 of synthesis example 29 e) arereacted according to synthesis example 20 d) with 398 mg (2.43 mmol) of(2-isopropylphenyl)boronic acid, 686 mg (3.23 mmol) of tripotassiumphosphate, 24.7 mg (0.03 mmol) oftris(dibenzylideneacetone)dipalladium(0), and 39.8 mg (0.10 mmol) of2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl, in 200 ml of tolueneand 40 ml of water, with a reaction time of 17 hours at 98° C., givingthe title product as a light yellow solid (yield: 0.49 g (59%)).

¹H-NMR (400 MHz, CD₂Cl₂): δ*=0.90 (m, 9H), 1.01 (m, 9H), 1.19 (m, 18H),2.09-2.38 (m, 12H), 2.85, 3.07 (2 m, 3H), 5.98-7.68 (very broad signal,9H), 6.51 (br. s, 3H), 6.76 (m, 3H), 7.23 (m, 6H), 7.41 (m, 6H), 8.05(m, 3H), 8.29 (m, 3H), 8.54 (m, 3H).

Synthesis Example 30. Synthesis of Complex (Y-2) a) Synthesis ofN2,N3-bis(4-isopropylphenyl)pyrazine-2,3-diamine

16.0 g (0.11 mol) of 2,3-dichloropyrazine are reacted according tosynthesis example 29 a) with 32.0 g (0.24 mol) of 4-isopropylaniline in200 ml of o-xylene under reflux during 12 hours, giving after workup andpurification the title product as a yellow solid (yield: 34.5 g (93%)).

¹H-NMR (300 MHz, d₄-MeOD): δ=1.14 (d, 12H), 4.46 (s, 2H), 7.08 (d, 4H),7.34 (m, 6 H).

b) Synthesis of[3-(4-isopropylanilino)pyrazin-2-yl]-(4-isopropylphenyl)ammoniumchloride

34.5 g (0.10 mol) of N2,N3-bis(4-isopropylphenyl)pyrazine-2,3-diamineare reacted according to synthesis example 29 b) with 300 ml of 37%aqueous hydrochloric, giving the title product as a light yellow solid(yield: 34.2 g, still wet)

¹H-NMR (400 MHz, d₆-DMSO): δ=1.23 (d, 12H), 2.91 (m, 2H), 7.32 (d, 4H),7.36 (s, 2H), 7.62 (d, 4H), 10.78 (br. s, 2H).

c) Synthesis of2-ethoxy-1,3-bis(4-isopropylphenyl)-2H-imidazo[4,5-b]pyrazine

34.2 g (ca. 89 mmol, still including some residual water) of[3-(4-isopropylanilino)-pyrazin-2-yl]-(4-isopropylphenyl)ammoniumchloride are reacted are reacted according to synthesis example 29 c)with 300 ml (1.8 mol) of triethyl orthoformate heated under argon at100° C. during 18 hours, giving the title product as a light yellowsolid (yield: 26.9 g (75%)).

¹H-NMR (300 MHz, d₆-DMSO): δ=0.91 (t, 3H), 1.23 (d, 12H), 2.91 (m, 2H),3.18 (m, 2H), 7.34 (d, 4H), 7.47 (s, 2H), 7.67 (s, 1H), 7.93 (d, 4H).

d) Synthesis of Complex Intermediate (CI-2)

5.75 g (14.3 mmol) of2-ethoxy-1,3-bis(4-isopropylphenyl)-2H-imidazo[4,5-b]pyrazine arereacted according to synthesis example 29 d) with 1.20 g (1.8 mmol) ofchloro(1,5-cyclooctadiene)iridium(I) dimer in 100 ml of o-xylene underreflux during eight hours, giving the title product as a yellow solid(yield: 2.03 g (45%)).

e) Synthesis of Bromo-Complex Intermediate (HI-7)

0.93 g (0.74 mmol) of the product of the synthesis example 30 d), arereacted according to synthesis example 29 e) with 320 mg (1.12 mmol) of1,3-dibromo-5,5-dimethylhydantoin in 100 ml of dichloromethane at 0° C.during 16 hours, giving the title product as a light yellow solid(yield: 0.94 g (85%)).

¹H-NMR (400 MHz, CD₂Cl₂): δ•=0.88 (d, 9H), 1.04 (m, 27H), 2.57 (m, 3H),3.23 (m, 3 H), 5.88-7.69 (3 broad signals, 12H), 6.53 (s, 3H), 8.12 (d,3H), 8.41 (d, 3H), 8.94 (s, 3 H).

f) Synthesis of Complex (Y-2)

389 mg (0.54 mmol) of the product, HI-7, of synthesis example 30 e) arereacted according to synthesis example 29 e) with 140 mg (1.15 mmol) ofphenylboronic acid, 0.32 g (1.5 mmol) of tripotassium phosphate, 11.6 mg(0.01 mmol) of tris(dibenzylideneacetone)dipalladium(0), and 19 mg (0.05mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl, in 95 ml oftoluene and 19 ml of water, with a reaction time of 23 hours underreflux, giving the title product as a light yellow solid (yield: 0.15 g(39%)).

¹H-NMR (400 MHz, CD₂Cl₂): δ•=0.89 (d, 9H), 0.99 (d, 9H), 1.03 (d, 9H),1.10 (d, 9H), 2.59 (m, 3H), 2.96 (m, 3H), 5.90-7.72 (3 broad signals,12H), 6.72 (m, 3H), 7.38 (m, 3H), 7.46 (m, 12H), 8.08 (d, 3H), 8.32 (d,3H), 8.61 (s, 3H).

Synthesis Example 31. Synthesis of Bromo-Complex Intermediates HI-5(Isomer 1, Isomer 2, Isomer 3 and Isomer 4) a) Synthesis of CC-5 (Isomer1, Isomer 2, Isomer 3 and Isomer 4)

A mixture of 5.0 g (13 mmol) intermediate G and 0.9 g (1.3 mmol)[Ir(cod)Cl]₂ in o-xylene (300 ml) is stirred at reflux for 5 h. Thesolvent is removed, the residue is taken up in a 1:1 mixture ofacetonitrile and acetone (100 ml) and stirred for 16h. The solid(containing CC-5 (Isomer 1, Isomer 2, Isomer 3 and Isomer 4)) isisolated by filtration. The synthesis of CC-5 (Isomer 1, Isomer 2,Isomer 3 and Isomer 4) is described in more detail in PCT/EP2014/064054.

The mixture of Isomer-1, Isomer-2, Isomer-3 and Isomer-4 of CC-5 (0.86g, 0.74 mmol) and iron(III) bromide (12.0 mg, 0.04 mmol) are dissolvedin 180 ml of dichloromethane under inert atmosphere. After cooling thesystem to 0° C., N-bromo succinimide (0.40 g, 2.22 mmol) is added andthe solution is stirred in the absence of light for 7 hours. A 10% watersolution of sodium bisulfite (6 ml) is added to the reaction mixture andstirred. After pouring the solution into water, the phases are separatedand the organic portion dried over anhydrous sodium sulfate. Afterfiltering, the solvent is evaporated and the solid residue purified bycolumn chromatography (SiO₂, dichloromethane/toluene) providing fourproduct isomers as yellow solids which have been further assigned by¹H-NMR analysis (combined yield of all four product isomers 1-4: 0.99 g(82%)).

HI-5 (Isomer 1): ¹H-NMR (400 MHz, CD₂Cl₂): δ=8.89 (d, 3H, J=1.96 Hz),8.43 (s, 3H), 8.03 (d, 3H, J=2.88 Hz), 7.65-5.85 (br m, 21H), 1.30 (s,27H)

HI-5 (Isomer 2): ¹H-NMR (400 MHz, CD₂Cl₂): δ=8.96 (d, 1H, J=1.97 Hz),8.90 (d, 1H, J=1.97 Hz), 8.87 (d, 1H, J=1.97 Hz), 8.44 (s, 1H), 8.42 (s,1H), 8.15 (s, 1H), 7.49-6.04 (brm, 21H), 1.56 (s, 9H), 1.32 (s, 9H),1.29 (s, 9H)

HI-5 (Isomer 3): ¹H-NMR (400 MHz, CD₂Cl₂): δ=8.98 (d, 1H, J=1.95 Hz),8.95 (d, 1H, J=1.95 Hz), 8.88 (d, 1H, J=1.95 Hz), 8.43 (s, 1H), 8.16 (s,1H), 8.14 (s, 1H), 7.70-6.07 (br m, 21H), 1.58 (s, 9H), 1.55 (s, 9H),1.31 (s, 9H)

HI-5 (Isomer 4): ¹H-NMR (400 MHz, CD₂Cl₂): δ=8.95 (d, 3H, J=1.96 Hz),8.16 (s, 3H), 7.75-5.98 (br m, 21H), 1.56 (s, 27H).

Synthesis Example 32. Synthesis of Complex (C′113 (Isomer 3))

HI-5 (Isomer 3) of synthesis example 31 (0.26 g, 0.18 mmol),2,6-diisopropylphenylboronic acid (0.13 g, 0.81 mmol), and K₃PO₄ (0.23g, 1.08 mmol) are suspended in 150 ml of toluene and 30 ml of water.Argon is bubbled through the solution for 30 minutes and thentris-(dibenzylidenacetone)-dipalladium(0) (8.0 mg, 0.03 mmol) and S-phos(13 mg, 0.03 mmol) are added. The solution is purged with argon for 15minutes and then heated to reflux under inert atmosphere overnight.After cooling to room temperature, phases are separated, the organicphase collected and the solvent removed. The solid is then purified viacolumn chromatography (silica, first purificationtoluene/dichloromethane, second purification cyclohexane/ethyl acetate).The title product is isolated as a yellow solid (yield: 0.15 g (54%)).

¹H-NMR (500 MHz, CD₂Cl₂): δ=8.82 (d, J=1.7 Hz, 1H), 8.80 (d, J=1.7 Hz,1H), 8.74 (d, J=1.7 Hz, 1H), 8.33 (s, 1H), 8.12 (s, 1H), 8.11 (s, 1H),7.40 (d, J=8.2 Hz, 3H), 7.34-7.29 (m, 6H), 7.20 (td, J=7.4, 1.5 Hz, 3H),7.14-6.29 (m, 21H), 3.40 (h, J=6.8 Hz, 2H), 3.31 (h, J=6.7 Hz, 1H), 1.48(s, 9H), 1.47 (s, 9H), 1.30 (s, 9H), 1.25-1.20 (m, 9H), 1.16-1.11 (m,9H).

Synthesis Example 33. Synthesis of Complex (M-4) a) Synthesis of3-aminodibenzofuran

Reference is made to preparation of compound (3) in WO2012/020327.

¹H-NMR (300 MHz, CDCl₃): δ=3.92 (br. s, 2H), 6.71 (dd, 1H), 6.87 (d,1H), 7.32 (m, 2H), 7.50 (d, 1H), 7.71 (d, 1H), 7.82 (d, 1H).

b) Synthesis of 2,4-dibromodibenzofuran-3-amine

21.7 g (118 mmol) of 3-aminodibenzofuran are dissolved in 200 ml of DMFand cooled down to ice-bath temperature under argon atmosphere. 43.0 g(242 mmol) of N-bromosuccinimide are added in small portions during 90minutes, letting the temperature not rise above 10° C. 100 ml ofadditional DMF are added at 8° C. and the temperature let rising to roomtemperature during one hour under stirring. The dark solution is treatedwith 30 ml aqueous sodium thiosulfate solution and diluted with water upto a volume of 2000 ml, followed by stirring during 20 minutes. Theresulting suspension is filtered and the solid mixed with 200 ml ofethanol and stirred during 15 minutes. The suspension is filtered andthe resulting solid washed with ethanol and dried under vacuum, givingthe title product as a light yellow solid (yield: 39.8 g (98%)).

¹H-NMR (400 MHz, d₆-DMSO): δ=4.80 (br. s, 2H), 7.34 (td, 1H), 7.41 (td,1H), 7.59 (d, 1 H), 7.78 (m, 1H), 7.96 (s, 1H).

c) Synthesis of 2,4-diisobutyldibenzofuran-3-amine

15.6 g (45.7 mmol) of 2,4-dibromodibenzofuran-3-amine are dissolvedunder in 220 ml of THF and 50 mg (0.22 mmol) of palladium(II) acetateand 200 mg (0.46 mmol) of2-dicyclohexylphosphino-2′,6′-bis(N,N-dimethylamino)biphenyl (=CPhos)are added.

The violet-brown solution is three times evacuated and backfilled withargon and cooled down to 0° C. 220 ml (0.11 mol) 0.5M isobutylzincbromide solution slowly added during one hour, and stirring continuedduring 30 minutes at 0° C. The temperature is let rising to roomtemperature and the dark brown solution further stirred during 17 hours.100 ml of water are added together with 10 g of Hyflo® filter aid, andstirred during 30 minutes. The brown suspension is filtered through a 3cm layer of Hyflo® filter aid followed by washing the filter aid withtoluene. The combined filtrates are concentrated. The brown residue isdiluted with 500 ml of toluene and the water phase separated. Theorganic phase is extracted with 200 ml of 2% aqueous 3-amino-1-propanolsolution, followed by extraction with 200 ml of water and 100 ml ofsaturated sodium chloride. The organic phase is dried over sodiumsulfate, filtered and concentrated under vacuum, giving the titleproduct as a red oil, which was used in the next step without furtherpurification (12.3 g, product content of 84% according to GCmeasurement).

d) Synthesis of 3-iodo-2,4-diisobutyl-dibenzofuran

3.79 g (10.8 mmol) of 2,4-diisobutyldibenzofuran-3-amine are dissolvedin 200 ml of tert-butanol followed by fast addition of a solution of9.26 g (48.7 mmol) of p-toluenesulfonic acid in 50 ml of water. Thelight yellow solution is stirred at room temperature during 15 minutes,and cooled down to 5° C. 2.25 g (32.6 mmol) and 6.70 g (40.4 mmol) ofpotassium iodide are dissolved in 100 ml of water and added to thereaction mixture slowly at a maximum temperature of 5° C. during onehour. The dark suspension is stirred at 0° C. during 30 minutes and thetemperature let rising to room temperature, followed by heating at 40°C. during 30 minutes. The reddish suspension is cooled down and 40 ml of20% aqueous sodium bicarbonate solution are added followed by theaddition of 100 ml of 10% aqueous sodium thiosulfate solution. Thecolorless suspension is poured onto 800 ml of an ice-water mixture understirring. The light grey suspension is filtered and he solid is washedwith water and ethanol, followed by drying under vacuum, giving thetitle product as a white solid (yield: 2.79 g (64%)).

¹H-NMR (400 MHz, CDCl₃): δ=1.04 (t, 12H), 2.11 (m, 1H), 2.29 (m, 1H),2.86 (d, 2H), 3.10 (d, 2H), 7.35 (td, 1H), 7.49 (td, 1H), 7.59 (d, 1H),7.62 (s, 1H), 7.95 (d, 1H).

e) Synthesis of (1,3-diisobutyldibenzofuran-2-yl)boronic acid

1.45 g (3.5 mmol) of 3-iodo-2,4-diisobutyl-dibenzofuran are dissolved in20 ml of THF under argon atmosphere and slowly treated with 1.68 ml (4.2mmol) of 2.5M n-butyl lithium solution in hexane at −77° C., letting thetemperature not rise above −70° C. during addition. The light yellowsolution is stirred at −78° C. during one hour. 0.70 g (6.7 mmol) oftrimethylborate are slowly added during 35 minutes, letting thetemperature not rise above −70° C., and stirring continued for one hourat −78° C. The temperature is let rising to room temperature understirring and the yellow solution slowly treated with 20 ml of water. 6ml of 6% aqueous hydrochloric acid are added and THF distilled off undervacuum at 80° C., followed by the addition of 15 ml of heptane andstirring at ice-bath temperature during one hour. The suspension isfiltered and the solid washed with heptane giving the title product as abeige solid (yield: 1.11 g (98%)).

¹H-NMR (400 MHz, d₆-DMSO): δ=0.91 (d, 12H), 1.98 (m, 1H), 2.14 (m, 1H),2.65 (d, 2H), 2.84 (d, 2H), 7.34 (td, 1H), 7.46 (td, 1H), 7.66 (m, 2H),8.07 (d, 1H), 8.22 (s, 2H).

f) Synthesis of Complex (M-4)

1.10 g (0.89 mmol) of bromo-complex product (HI-1) of synthesis example6, are reacted according to synthesis example 20 d) with 1.12 g (3.45mmol) of (1,3-diisobutyldibenzofuran-2-yl)boronic acid, 1.16 g (5.41mmol) of tripotassium phosphate, 41 mg (0.04 mmol) oftris(dibenzylideneacetone)dipalladium(0), and 67 mg (0.16 mmol) of2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl, in 70 ml of toluene and16 ml of water, with a reaction time of 17 hours at 90° C. The resultingorange emulsion is diluted with 30 ml of dichloromethane and the organicphase stirred with 15 ml of 5% aqueous sodium cyanide solution. Thelight yellow organic phase is separated and filtered through a 3 cmlayer of silica gel followed by rinsing the silica gel withdichloromethane. The combined eluents are concentrated under vacuum andthe resulting solid separated and washed with ethanol and heptane,followed by drying under vacuum, giving the title product as a lightyellow solid (yield: 1.23 g (78%)).

¹H-NMR (400 MHz, CD₂Cl₂): δ8=0.65 (m, 18H), 0.86 (m, 18H), 1.83 (m, 3H),2.05 (m, 3 H), 2.38-2.98 (m, 12H), 6.27-7.90 (broad signal, 12H), 6.77(m, 3H), 6.90 (t, 3H), 7.01 (d, 3H), 7.38 (t, 3H), 7.48 (t, 3H), 7.61(dd, 3H), 7.75 (d, 3H), 8.02 (m, 3H), 8.10 (t, 3H), 8.30 (d, 3H), 8.77(d, 3H).

II. PHOTOLUMINESCENCE EXAMPLES

Determination of the Photoluminescence Spectra (2% Film in PMMA Matrix)

The photoluminescence (PL) spectra of the complexes are measured on thinpolymer films doped with the respective complexes. The thin films areprepared by the following procedure: a 10%-w/w polymer solution is madeby dissolving 1 g of the polymer “PMMA 6N” (Evonik) in 9 g ofdichloromethane, followed by stirring for one hour. 2 mg of therespective complexes are added to 0.098 g of the PMMA solution, andstirring continued for one minute. The solutions are casted bydoctor-blading with a film applicator (Model 360 2082, Erichsen) with a60 μm gap onto quartz substrates providing thin doped polymer films(thickness ca. 6 μm). The PL spectra and quantum-yields (Q.Y.) of thesefilms are measured with the integrating-sphere method using the AbsolutePL Quantum Yield Measurement System (Hamamatsu, Model C9920-02)(excitation wavelength: 370 nm).

Determination of the Lifetime of Luminescence τ_(V)

The lifetime (τ_(V)) of the luminescence of the complexes in theprepared films are measured by the following procedure: For excitationof the emission a sequence of short laser pulses (THG Nd-YAG, 355 nm, 1nsec pulse length, 1 kHz repetition rate) is used. The emissions aredetected by the time-resolved photon-counting technique in themulti-channel scaling modus using a combination of photomultiplier,discriminator and a multiscaler card (FAST ComTec GmbH, Model P7888).

The PL Q.Y., λ_(max), CIE x, y, and τ_(V) values of thephotoluminescence measurements are included in the following tables.

PL λ_(max) τv Cpd. Formula Q.Y. (nm) CIE x, y (μs) CC-1

93% 474 0.15, 0.25 2.37 A-17

95% 476 0.16, 0.28 1.95 B-43

95% 476 0.16, 0.27 1.94 A-15

88% 476 0.16, 0.28 1.95 B-15

96% 478 0.16, 0.27 1.99 E-1

79% 485 0.18, 0.37 1.84 A-1

87% 477 0.16, 0.28 1.78 C-125

91% 480 0.16, 0.31 1.65 C-126

94% 477 0.16, 0.28 1.67 C-127

94% 478 0.16, 0.29 1.69 G-1

88% 464 0.15, 0.16 2.16 C-161

98% 477 0.16, 0.28 1.78 C-130

93% 477 0.16, 0.28 1.86 C-128

87% 477 0.16, 0.28 1.41 A-6

95% 478 0.16, 0.29 1.81 A-2

94% 477 0.16, 0.28 1.82 Y-1

92% 484 0.17, 0.34 1.96 Y-2

96% 485 0.17, 0.36 1.90 M-4

95% 473 0.15, 0.24 1.97 A-3

90% 475 0.16, 0.26 1.77 A-14

87% 479 0.16, 0.30 1.64

-   The inventive metal carbene complexes show a blue emission, with    very high absolute quantum efficiency, and with improved (=shorter)    lifetime of luminescence in comparison with comparative compound    CC-1.

PL λ_(max) • τ_(v) Cpd. Formula Q.Y. (nm) CIE x, y (μs) CC-2

95% 473 0.15, 0.23 5.74 A-85

91% 474 0.15, 0.25 4.12

The inventive metal carbene complex A-85 shows a blue emission, withvery high absolute quantum efficiency, and with improved (=shorter)lifetime of luminescence in comparison with comparative compound CC-2.

PL λ_(max) • τ_(v) Cpd. Formula Q.Y. (nm) CIE x, y (μs) CC-3

89% 482 0.17, 0.32 2.43 J-113

89% 485 0.18, 0.36 1.84 L-1

94% 476 0.15, 0.26 1.96

The inventive metal carbene complexes, J-113 and L-1, show a blueemission, with very high absolute quantum efficiency, and with improved(=shorter) lifetime of luminescence in comparison with comparativecompound CC-3.

PL λ_(max) • τ_(v) Cpd. Q.Y. (nm) CIE x, y (μs) CC-5

99% 467 0.14, 0.19 2.90 C′-113 (Isomer 3)

84% 469 0.15, 0.21 1.84

The inventive metal carbene complex, C′-113 (Isomer 3), shows a blueemission, with very high absolute quantum efficiency, and with improved(=shorter) lifetime of luminescence in comparison with comparativecompound CC-5 (Isomer 3) of Synthesis Example 31 a)).

Determination of the photoluminescence Spectra (4% film in host SH-5)

SH-5:

described in WO2010/079051, structure on page 22 (X═O); synthesis as inexample 17 in EP1885818 on page 104 in US2013/0119360.

The photoluminescence (PL) spectra of the iridium complexes are measuredon thin SH-5 films doped with 4%-w/w of the respective iridiumcomplexes. The thin film samples are prepared by the followingprocedure: 1 mg of the respective iridium complexes and 24 mg of SH-5are added to 2.5 mL of dichloromethane and the mixtures stirred for 1-5minutes. The resulting solutions are casted by doctor-blading with afilm applicator (Model 360 2082, Erichsen) with a 30 μm gap onto quartzsubstrates. The PL spectra are measured as described for the PMMA films(excitation wavelength: 370 nm). The lifetime (τ_(V)) of thephosphorescence of the iridium complexes in the prepared films aremeasured as described for the PMMA films The PL Q.Y., λ_(max), CIE x, yand FWHM of the iridium complex doped α-NPD films are shown in the tablebelow:

The PL Q.Y., λ_(max), CIE x, y, and τ_(V) values of thephotoluminescence measurements are included in the following tables.

PL λ_(max) τ_(v) Cpd. Formula Q.Y. (nm) CIE x, y (μs) CC-1

90% 473 0.15, 0.24 1.82 A-17

94% 473 0.14, 0.24 1.37 B-43

87% 476 0.15, 0.25 1.49 A-15

79% 476 0.15, 0.26 1.33 B-15

93% 479 0.15, 0.27 1.58 C-125

82% 480 0.15, 0.30 1.23 C-126

88% 479 0.15, 0.29 1.24 C-127

83% 477 0.15, 0.27 1.26 C-161

96% 479 0.15, 0.28 1.18 C-130

82% 478 0.15, 0.27 1.33 A-6

85% 479 0.15, 0.28 1.34 A-2

88% 478 0.15, 0.26 1.31 X-1

79 476 0.15, 0.27 1.40 X-2

87 473 0.14, 0.24 1.59 Y-1

87% 483 0.15, 0.32 1.45 Y-2

95% 481 0.16, 0.31 1.70 M-4

77% 472 0.15, 0.23 1.30 A-2

79% 475 0.15, 0.24 1.39 A-14

81% 474 0.15, 0.25 1.22

The inventive metal carbene complexes show a blue emission, with veryhigh absolute quantum efficiency, and with improved (=shorter) lifetimeof luminescence in comparison with comparative compound CC-1.

III. DEVICE EXAMPLES

Production of an OLED (General Procedure)

The ITO substrate used as the anode is cleaned first with commercialdetergents for LCD production (Deconex® 20NS, and 25ORGAN-ACID®neutralizing agent) and then in an acetone/isopropanol mixture in anultrasound bath. To eliminate possible organic residues, the substrateis exposed to a continuous ozone flow in an ozone oven for a further 25minutes. This treatment also improves the hole injection properties ofthe ITO. Next, the hole injection layer (40 nm) AJ20-1000 from Plexcoreis spun on from solution.

Thereafter, the organic materials specified below are applied by vapordeposition to the cleaned substrate at about 10⁻⁷-10⁻⁹ mbar at a rate ofapprox. 0.5-5 nm/min. The hole conductor and exciton blocker applied tothe substrate is Ir(DPBIC)₃ (devices 1 to 3) with a thickness of 20 nm,of which the first 10 nm are doped with MoO_(x) (50 wt.-%:50 wt.-%) toimprove the conductivity.

(for preparation of Ir(DPBIC)₃ see Ir complex (7) in the applicationWO2005/019373).

Subsequently, a mixture of emitter, Ir(DPBIC)₃ and a host material (theemitter (A-17 or B-15), the host material (SH-1, SH-2, or SH-5) and therelative amounts in % by weight are given in the specific deviceexamples) is applied by vapor deposition with a thickness of 40 nm(devices 1 to 3). Subsequently, the host material is applied by vapordeposition with a thickness of 5 nm as an exciton and hole blocker.

Host Material:

SH-1:

(described in WO2009/008100, example 4)

SH-2:

(compound “3-1” in “Synthetic example 2” in US2009/066226)

SH-5:

described in WO2010/079051, structure on page 22 (X═O); synthesis as inexample 17 in EP1885818 on page 104 in US2013/0119360.

Next, as an electron transporter, a mixture of Liq and ETM (ETM-1 asspecified in the specific device examples) (50 wt.-%:50 wt.-%) isapplied by vapor deposition in a thickness of 25 nm; then a 4 nm LiFlayer is applied; and finally a 100 nm-thick Al electrode is applied.All components are adhesive-bonded to a glass lid in an inert nitrogenatmosphere.

Electron Transport Material:

ETM-2:

(compound A1 in WO 2011/157779; compound A-10 in WO2006/128800)

To characterize the OLED, electroluminescence spectra are recorded atdifferent currents and voltages. In addition, the current-voltagecharacteristic is measured in combination with the light output emitted.The light output can be converted to photometric parameters bycalibration with a photometer. The CIE_(x,y) coordinates are extractedfrom the spectra according to CIE 1931 as known in the art.

Device 1:

HIL Plexcore AJ20-1000-10 nm Ir(DPBIC)₃:MoO₃ (50:50)-10 nm Ir(DPBIC)₃-40nm blue emitter/SH-2/Ir(DPBIC)₃ (10:80:10)-5 nm SH-2-25 nm ETM-2:Liq(50:50)-4 nm KF-100 nm Al

Device 2:

HIL Plexcore AJ20-1000-10 nm Ir(DPBIC)₃:MoO₃ (50:50)-10 nm Ir(DPBIC)₃-40nm blue emitter/SH-1/Ir(DPBIC)₃ (10:80:10)-5 nm SH-1-25 nm ETM-2:Liq(50:50)-4 nm KF-100 nm Al

Device 3:

HIL Plexcore AJ20-1000-10 nm Ir(DPBIC)₃:MoO₃ (50:50)-10 nm Ir(DPBIC)₃-40nm blue emitter/SH-5/Ir(DPBIC)₃ (10:80:10)-5 nm SH-5-25 nm ETM-2:Liq(50:50)-4 nm KF-100 nm Al

For the different emitters and different host materials in theabove-described OLED structure, the following electrooptical data areobtained (all data at 300 nits):

Blue Voltage currEff LumEff emitter [V] [cd/A] [lm/W] EQE [%] CIE x, yDevice 1.1 A-17 5.1 27.7 17.0 13.9 0.16, 0.30 Device 1.2 B-15 4.4 29.921.3 14.5 0.17, 0.32 Device 2 A-17 5.4 29.0 16.9 14.8 0.16, 0.30 Device3 B-15 4.1 29.5 22.5 15.3 0.16, 0.29

The devices comprising the inventive metal carbene complexes show a blueemission color with high efficiency and low voltage.

Device 4:

80 nm Ir(DPBIC)₃:MoO₃ (90:10)-10 nm Ir(DPBIC)₃-40 nm blueemitter/SH-2/Ir(DPBIC)₃ (20:70:10)-5 nm SH-2-25 nm ETM-2:Liq (50:50)-4nm KF-100 nm Al

Device 5:

100 nm Ir(DPBIC)₃:MoO₃ (90:10)-10 nm Ir(DPBIC)₃-20 nm blueemitter/SH-2/Ir(DPBIC)₃ (20:70:10)-5 nm SH2-35 nm ETM-2:Liq (50:50)-4 nmKF-100 nm Al

The device lifetime LT₇₀ of the diode is defined by the time taken forthe luminance to fall to 70% of its initial value. The lifetime ismeasured at LT₇₀ at 4000 cd/m² and then calculated back to LT₇₀ at 300cd/m² using the experimentally observed acceleration factor. Thelifetime measurement is carried out at a constant current. All otherdata are obtained directly at 300 nits.

For the different emitters in the above-described OLED structures, thefollowing electrooptical data are obtained, wherein the measured valuesof voltage, current efficiency, luminance efficacy, EQE and lifetime ofthe device 4.1 are set to 100 and the values of the devices 4.2, 5.1 and5.2 are specified in relation to those of device 4.1:

Rel. Rel. Rel. Rel. Rel. Blue λ_(max) Voltage currEff LumEff EQE¹⁾Lifetime²⁾ emitter CIE x, y [nm] [%] [%] [%] [%] (%) Device CC-1 0.16,498 100 100 100 100 100 4.1 0.29 Device C-127 0.16, 500 110 109 98 104168 4.2 0.31 Device CC-1 0.16, 497 75 108 145 110 101 5.1 0.28 DeviceC-127 0.16, 499 81 111 141 111 173 5.2 0.30 ¹⁾External quantumefficiency (EQE) is # a of generated photons escaped from a substance ora device/# of electrons flowing through it. ²⁾Drop to 70% of initialluminance.

The devices 4.2 and 5.2 comprising the inventive metal carbene complexC-127 show a blue emission color with high efficiency and low voltage,together with increased device lifetime LT₇₀ in comparison to thedevices comprising the comparative metal carbene complex CC-1. Referenceis made to FIG. 1, which provides a plot of the EL intensity ofcompounds CC-1 and C-127 as a function of wavelength.

1.-23. (canceled)
 24. A metal-carbene complex of the general formula

M is Pt; m is 1, or 2; o is 0, or 1; and the sum of m and o is 2; L is amonoanionic bidentate ligand; R is a group of formula

R′ is hydrogen, C₁-C₈alkyl group, or a fluoroC₁-C₄alkyl group; R¹ ishydrogen, a C₁-C₈alkyl group, a fluoroC₁-C₄alkyl group, or aC₃-C₆cycloalkyl group; R² is hydrogen, a C₁-C₈alkyl group, afluoroC₁-C₄alkyl group, or a C₃-C₆cycloalkyl group; R³, R^(3′) andR^(3″) are independently of each other hydrogen; a C₁-C₁₈alkyl group,which can optionally be substituted by E and/or interrupted by D; aC₃-C₁₂cycloalkyl group, which can optionally be substituted by G; aC₃-C₁₀heterocycloalkyl radical which is interrupted by at least one ofO, S and NR⁶⁵ and/or substituted by E; a C₆-C₁₄aryl group, which canoptionally be substituted by G; or a C₂-C₃₀heteroaryl group, which canoptionally be substituted by G; a halogen atom, CF₃, CN, or SiR⁸⁰R⁸¹R⁸²;R³ and R^(3′), or R¹ and R^(3′) together form a group of formula

 wherein X is O, S, NR⁷⁵ or CR⁷³R⁷⁴; R⁴, R^(4′) and R⁵ are independentlyof each other hydrogen; a C₁-C₁₈alkyl group, which can optionally besubstituted by E and/or interrupted by D; a C₃-C₁₂cycloalkyl group,which can optionally be substituted by G; a C₃-C₁₀heterocycloalkylradical which is interrupted by at least one of O, S and NR⁶⁵ and/orsubstituted by E; a C₆-C₁₄aryl group, which can optionally besubstituted by G; or a C₂-C₃₀heteroaryl group, which can optionally besubstituted by G; a halogen atom, CF₃, CN, or SiR⁸⁰R⁸¹R⁸²; or R⁴ andR^(4′) together form a group of formula, or

R⁶ and R⁷ are independently of each other hydrogen, a C₁-C₈alkyl group,optionally interrupted by at least one heteroatom selected from —O—, —S—and —NR⁶⁵—, optionally bearing at least one substituent, which isselected from the group consisting of C₁-C₈alkyl, C₁-C₈alkoxy, halogen,and C₁-C₈haloalkyl; a C₃-C₆cycloalkyl group, optionally bearing at leastone substituent, which is selected from the group consisting ofC₁-C₈alkyl, C₁-C₈alkoxy, halogen, and C₁-C₈haloalkyl; a heteroC₃-C₆cycloalkyl group, interrupted by at least one heteroatom selected from —O—,—S— and —NR⁶⁵—, optionally bearing at least one substituent, which isselected from C₁-C₈alkyl, C₁-C₈alkoxy, halogen, and C₁-C₈haloalkyl; or aC₆-C₁₄arylgroup, which can optionally be substituted by one, or twoC₁-C₈alkyl groups; or R⁶ and R⁷ form together a ring

wherein A²¹, A^(21′), A²², A^(22′), A²³, A^(23′), A^(24′) and A²⁴ areindependently of each other hydrogen, a C₁-C₄alkyl group, aC₃-C₆cycloalkyl group, or a fluoroC₁-C₄alkyl group; D is —CO—, —COO—,—S—, —SO—, —SO₂—, —O—, —NR⁶⁵—, —SiR⁷⁰R⁷¹—, —POR⁷²—, —CR⁶³═CR⁶⁴— or —C≡C;E is —OR⁶⁹, —SR⁶⁹, —NR⁶⁵R⁶⁶, —COR⁶⁸, —COOR⁶⁷, —CONR⁶⁵R⁶⁶, —CN, or F; Gis E; or a C₁-C₁₈alkyl group; a C₆-C₁₄aryl group, which is optionallysubstituted by a substituent selected from the group consisting of F,C₁-C₁₈alkyl, which is optionally substituted by F and C₁-C₁₈alkyl, whichis interrupted by O; a C₂-C₁₀heteroaryl group; or a C₂-C₁₀heteroarylgroup, which is substituted by a substituent selected from the groupconsisting of F, C₁-C₁₈alkyl, which is optionally substituted by F,SiR⁸⁰R⁸¹R⁸², and C₁-C₁₈alkyl, which is interrupted by O; R⁶³ and R⁶⁴ areindependently of each other hydrogen; a C₆-C₁₈aryl group, which isoptionally substituted by a substituent selected from the groupconsisting of C₁-C₁₈alkyl and C₁-C₁₈alkoxy; or a C₁-C₁₈alkyl group,which is optionally interrupted by —O—; R⁶⁵ and R⁶⁶ are independently ofeach other a C₆-C₁₈aryl group, which is optionally substituted by asubstituent selected from the group consisting of C₁-C₁₈alkyl andC₁-C₁₈alkoxy; or a C₁-C₁₈alkyl group, which is optionally interrupted by—O—; or R⁶⁵ and R⁶⁶ together form a 5-membered ring or 6-membered ring;R⁶⁷ is a C₆-C₁₈aryl group, which is optionally substituted by asubstituent selected from the group consisting of C₁-C₁₈alkyl andC₁-C₁₈alkoxy; or a C₁-C₁₈alkyl group which is optionally interrupted by—O—, R⁶⁸ is hydrogen; a C₆-C₁₈aryl group, which is optionallysubstituted by a substituent selected from the group consisting ofC₁-C₁₈alkyl and C₁-C₁₈alkoxy; or a C₁-C₁₈alkyl group, which isoptionally interrupted by —O—; R⁶⁹ is a C₆-C₁₈aryl group, which isoptionally substituted by a substituent selected from the groupconsisting of C₁-C₁₈alkyl and C₁-C₁₈alkoxy; or a C₁-C₁₈alkyl group,which is optionally interrupted by —O—; R⁷⁰ and R⁷¹ are independently ofeach other a C₁-C₁₈alkyl group; or a C₆-C₁₈aryl group, which isoptionally substituted by C₁-C₁₈alkyl; and R⁷² is a C₁-C₁₈alkyl group;or a C₆-C₁₈aryl group, which is optionally substituted by C₁-C₁₈alkyl;R⁷³ and R⁷⁴ are independently of each other hydrogen; a C₁-C₂₅alkylgroup, which is optionally interrupted by —O—; a C₇-C₂₅arylalkyl group;a C₆-C₂₄aryl group, which is optionally substituted by C₁-C₁₈alkyl; or aC₂-C₂₀heteroaryl group, which is optionally substituted by C₁-C₁₈alkyl;or R⁷³ and R⁷⁴ together form a 5-membered ring or 6-membered ring, whichis optionally substituted by a C₁-C₁₈alkyl group, which is optionallyinterrupted by —O—, or R⁷³ and R⁷⁴ together form a group of formula═CR⁷⁶R⁷⁷, wherein R⁷⁶ and R⁷⁷ are independently of each other hydrogen;a C₁-C₁₈alkyl group, which is optionally interrupted by O; a C₆-C₂₄arylgroup, which is optionally substituted by C₁-C₁₈alkyl; or aC₂-C₂₀heteroaryl group, which is optionally substituted by C₁-C₁₈alkyl;or R⁷⁵ is a C₆-C₁₈aryl group which is optionally substituted by asubstituent selected from the group consisting of C₁-C₁₈alkyl andC₁-C₁₈alkoxy; or a C₁-C₁₈alkyl group, which is optionally interrupted by—O—; and R⁸⁰, R⁸¹ and R⁸² are independently of each other a C₁-C₂₅alkylgroup, which is optionally interrupted by —O—; a C₆-C₁₄aryl group, whichis optionally substituted by C₁-C₁₈alkyl; or a C₂-C₁₀heteroaryl group,which is optionally substituted by C₁-C₁₈alkyl.
 25. The metal-carbenecomplex according to claim 24, which is a metal carbene complex offormula (II):

wherein R is a group of formula

 and R′ is hydrogen, or a C₁-C₅alkyl group.
 26. The metal complexaccording to claim 24, which is a metal complex of formula (IIa),formula (IIb), or formula (IIc):

wherein R is a group of formula

 and R⁶ in formula (IIa) is a C₁-C₈alkyl group, optionally interruptedby at least one heteroatom selected from —O—, —S— and —NR⁶⁵—, optionallybearing at least one substituent, which is selected from the groupconsisting of C₁-C₈alkyl, C₁-C₈alkoxy, halogen, and C₁-C₈haloalkyl; aC₃-C₆cycloalkyl group, optionally bearing at least one substituent,which is selected from the group consisting of C₁-C₈alkyl, C₁-C₈alkoxy,halogen, and C₁-C₈haloalkyl; a heteroC₃-C₆cycloalkyl group, interruptedby at least one heteroatom selected from —O—, —S— and —NR⁶⁵—, optionallybearing at least one substituent, which is selected from C₁-C₈alkyl,C₁-C₈alkoxy, halogen, and C₁-C₈haloalkyl; or a group of formula

 wherein (i) R²², R²³, and R²⁴ are independently of each other ahydrogen or a C₁-C₅alkyl group, with the proviso that only one or two ofR²², R²³, and R²⁴ may be a C₁-C₅alkyl group; (ii) R²⁵, R²⁶, and R²⁷ areindependently of each other a hydrogen or a C₁-C₅alkyl group, with theproviso that only one or two of R²⁵, R²⁶, and R²⁷ may be a C₁-C₅alkylgroup; or R⁶ and R⁷ in formula (IIc) form together a ring


27. The metal-carbene complex according to claim 24, wherein: R is agroup of formula

 wherein R¹ and R² are independently of each other a C₁-C₅alkyl group, acyclopentyl group or a cyclohexyl group; and R³ is hydrogen, C₁-C₅alkylgroup, a group of formula

 wherein R¹⁰ is hydrogen, or a C₁-C₅alkyl group; R¹¹ is hydrogen, or aC₁-C₅alkyl group; R¹² is a C₁-C₅alkyl group; and R^(12′) is a C₁-C₅alkylgroup.
 28. The metal complex according to claim 24, wherein R is a groupof formula

wherein R² is CF₃, a C₁-C₅alkyl group, a cyclopentyl group or acyclohexyl group; R³ is hydrogen, a C₁-C₅alkyl group, a cyclopentylgroup or a cyclohexyl group; and R^(3′) is hydrogen, a C₁-C₅alkyl group,a cyclopentyl group or a cyclohexyl group; with the proviso that in caseone of R³ and R^(3′) is a cyclopentyl group or a cyclohexyl group, theother is hydrogen.
 29. The metal complex according to claim 24, whereinR is a group of formula

wherein R³ is hydrogen, or a C₁-C₅alkyl group; R^(3′) is hydrogen, aC₁-C₅alkyl group, a cyclopentyl group or a cyclohexyl group; and R^(3′)is hydrogen, a C₁-C₅alkyl group, a cyclopentyl group or a cyclohexylgroup; with the proviso that if both R^(3′) and R^(3″) are independentlya C₁-C₅alkyl group, a cyclopentyl group or a cyclohexyl group, then R³is hydrogen.
 30. The metal-carbene complex according to claim 24,wherein (i) R⁴ is hydrogen, or a C₁-C₅alkyl group; R^(4′) is hydrogen;and R⁵ is hydrogen, or a C₁-C₅alkyl group; or (ii) R⁴ is hydrogen, or aC₁-C₅alkyl group; R^(4′) is a group of

 wherein R²⁰ is hydrogen, or a C₁-C₅alkyl group; R²¹ is hydrogen, or aC₁-C₅alkyl group; R²² is a C₁-C₅alkyl group; and R^(22′) is a C₁-C₅alkylgroup; and R⁵ is hydrogen, or a C₁-C₅alkyl group; or (iii) R⁴ ishydrogen; R^(4′) is a group of formula

 wherein R²² and R^(22′) are independently a C₁-C₅alkyl group; and R⁵ ishydrogen.
 31. The metal-carbene complex according to claim 24, wherein(i) R⁴ is hydrogen; R^(4′) is hydrogen, or a C₁-C₅alkyl group; and R⁵ ishydrogen, or C₁-C₅alkyl group; or (ii) R⁴ is hydrogen; R^(4′) ishydrogen; and R⁵ is a group of formula

 wherein R²⁰ is hydrogen, or a C₁-C₅alkyl group; R²¹ is hydrogen, or aC₁-C₅alkyl group; R²² is a C₁-C₅alkyl group; and R^(22′) is a C₁-C₅alkylgroup.
 32. The metal-carbene complex according to claim 24, wherein R⁶and R⁷ are independently of each other hydrogen, a C₁-C₈alkyl group, ora C₃-C₆cycloalkyl group; or R⁶ and R⁷ form together a ring

 with the proviso that if one of R⁶ and R⁷ is a C₃-C₆cycloalkyl group,the other is hydrogen.
 33. The metal-carbene complex according to claim24, wherein L is


34. The metal complex according to claim 24, wherein L is formula (D′):

which is different from formula (D)

wherein Z¹ and Z² are independently of each other N; or Z¹ and Z² areindependently of each other CH; R* is R′; R⁵⁴ is R⁴; R^(54′) is R^(4′);R⁵⁵ is R⁵; R⁵⁶ is R⁶; and R⁵⁷ is R⁷; wherein each group R is the samewithin one metal-carbene complex.
 35. An organic electronic devicecomprising at least one metal-carbene complex according to claim
 24. 36.A light-emitting layer comprising at least one metal-carbene complexaccording to claim
 24. 37. An apparatus selected from the groupconsisting of a stationary visual display unit, an information panel, amobile visual display unit, an illumination unit, a keyboard, an item ofclothing, a piece of furniture, and a wallpaper comprising the organicelectronic device according to claim 35, or the emitting layer accordingto claim
 36. 38. An apparatus selected from the group consisting of anelectrophotographic photoreceptor, a photoelectric converter, an organicsolar cell, a switching element, an organic light emitting field effecttransistor, an image sensor, a dye laser and an electroluminescentdevice comprising the metal-carbene complex according to claim
 24. 39. Aprocess for preparing a metal-carbene complex of the formula (I)according to claim 24:

wherein m is 2, and M, R, R′, R⁴, R^(4′), R⁵, R⁶ and R⁷ are as definedin claim 24; which process comprises: reacting a compound of formula(X):

wherein X¹ is CI, Br, or I; and m, M, R, R′, R⁴, R^(4′), R⁵, R⁶ and R⁷are as defined in claim 24; with a compound of the formula:

wherein: Y is: (a) —B(OH)₂, —B(OY¹)₂,

 wherein: each Y¹ is independently a C₁-C₁₀alkyl group; Y² is aC₂-C₁₀alkylene group; Y¹³ is hydrogen or a C₁-C₁₀alkyl group; and Y¹⁴ ishydrogen or a C₁-C₁₀alkyl group; (b) —SnR³⁰⁷R³⁰⁸R³⁰⁹, wherein: R³⁰⁷,R³⁰⁸ and R³⁰⁹ are independently hydrogen or C₁-C₆alkyl, wherein twoC₁-C₆alkyl radicals may optionally form a common ring; (c) ZnR³¹⁰R³¹¹,wherein: R³¹⁰ is halogen; and R³¹¹ is a C₁-C₁₀alkyl group, a C₆-C₁₂arylgroup, or a C₂-C₁₀alkenyl group; or (d) SiR³¹²R³¹³R³¹⁴, wherein: R³¹²,R³¹³ and R³¹⁴ are independently halogen, or a C₁-C₆alkyl group; and R¹,R², R³, R^(3′), and R^(3″) are as defined in claim
 24. 40. The processaccording to claim 39, which process further comprises: reacting acompound of formula (XI):

wherein: m, M, R¹, R⁴, R^(4′), R⁵, R⁶ and R⁷ are as defined in claim 39;with a halogenating agent to obtain a compound of formula (X):


41. A process for preparing metal carbene complexes, the processcomprising contacting a compound comprising a metal with at least oneligand of formula (D):

wherein R, R′, R⁴, R^(4′), R⁵, R⁶ and R⁷ are as defined in claim 24.